Resin composition

ABSTRACT

A resin composition comprising (A) an ethylene-vinyl alcohol copolymer, (B) a polyamide resin, (C) an ethylene-unsaturated carboxylic acid random copolymer or its metal salt, and (D) a thermoplastic resin except the resins noted above, of which the solubility parameter (as calculated from the Fedors&#39; formula) is not more than 11. The resin composition has good compatibility, excellent barrier properties, mechanical strength, flexibility, drawability, melt stability, scrap recyclability, heat sealability, coatability, stain resistance and transparency.

TECHNICAL FIELD

The present invention relates to a resin composition comprising (A) anethylene-vinyl alcohol copolymer, (B) a polyamide resin, (C) anethylene-unsaturated carboxylic acid random copolymer or its metal salt,and (D) a thermoplastic resin except the resins noted above, of whichthe solubility parameter (as calculated from the Fedors' formula) is notmore than 11. The resin composition has good compatibility, and hasexcellent barrier properties, mechanical strength, flexibility,drawability, melt stability, scrap recyclability, heat sealability,coatability, stain resistance and transparency.

BACKGROUND ARTS

As having excellent melt moldability, secondary

processability, mechanical characteristics and economical efficiency,hydrophobic thermoplastic resins such as polyolefins and polystyrenesare widely used for various applications. For example, in the field offood packaging industry, they are used for producing films andcontainers such as bottles, cups, etc.; while in the field of non-foodindustry, they are used in various daily necessities, parts of electricor electronic appliances for household use, car parts, etc.Multi-layered structures comprising hydrophobic thermoplastic resin andethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH) arewidely used in the field of food industry or the like that requiresbarrier properties to oxygen, flavors, etc.

Laminating hydrophobic thermoplastic resin and EVOH makes it possible toproduce laminate structures having the characteristics of the two. Apartfrom this, techniques of blending the two are also widely employed invarious fields.

However, EVOH is a resin having high hydrophilicity, and itscompatibility with hydrophobic thermoplastic resins is poor. Therefore,combining EVOH with hydrophobic thermoplastic resin is often problematicin that resin compositions having good physical properties could not beobtained. Various types of compatibilizers for the two, such astypically polyolefinic resins having polar functional groups haveheretofore been studied, but their effects are not always satisfactory.In that situation, it is desired to develop more effectivecompatibilizers capable of satisfactorily compatibilizing the two.

The technique of laminating hydrophobic thermoplastic resin suchpolyolefin or polystyrene with EVOH is useful, but is often problematicin producing complicated or small-sized laminates, since it is difficultto produce them through multi-layered lamination using the two. In thatsituation, it is desired to develop thermoplastic resins capable ofbeing formed into single-layered barrier structures. Japanese PatentApplication Laid-Open (JP-A) Hei-6-80150 (European Patent 584,808)discloses one example of a single-layered barrier structure, in which isused a resin composition comprising three components of polyolefin, EVOHhaving a melting point of not lower than 135° C. and EVOH having amelting point of 130° C. or lower, for producing the head of a two-piecetube container composed of a head and a cylindrical body. However, thehead disclosed therein is not still satisfactory, as its characteristicsincluding barrier properties, mechanical strength and adhesion strengthto cylindrical bodies are not always good.

Hydrophobic thermoplastic resins such as polyolefins, polystyrenes andthe like have various drawbacks owing to their hydrophobic properties.For example, when articles of those resins are painted, the adhesionstrength between their surfaces and paint vehicles (that is, thecoatability of their surfaces with paint vehicles) is poor since thesurfaces have non-polar properties. One drawback of the resins is thatthe resin articles must be subjected to primer treatment prior tocoating in order to improve the coatability of their surfaces, therebyresulting in that the coating costs are high. Recently, organicsolvent-based paints are being replaced by aqueous paints for theprotection of the environment. However, the compatibility of aqueouspaints with hydrophobic thermoplastic resins is extremely low. In thatsituation, it is much more desired to develop thermoplastic resins withimproved coatability.

On the other hand, EVOH is known to be useful in the field of foodindustry that requires barrier properties to oxygen, odors, flavors orthe like, for example, as wrapping or packaging films for foods, etc.

At present, however, EVOH is used little by itself, as its toughness ispoor. For example, one drawback of EVOH films is that they often havepin holes when repeatedly folded or deformed.

In order to overcome its poor toughness and flexibility, EVOH is oftenformed into multi-layered structures by laminating layers of EVOH andthermoplastic resin such as polyethylene, polypropylene, polyamide orthe like, along with layers of adhesive resin. However, as so mentionedhereinabove, it is often difficult to produce complicated orsmall-sized, multi-layered structures of thermoplastic resin and EVOH.Therefore, EVOH is often used by itself to form single-layeredstructures for complicated or small-sized articles. Even ifmulti-layered structures composed of EVOH and thermoplastic resin layersare formed, their applications are often limited since their propertiesare not good because of the poor flexibility of the EVOH resin layer.Accordingly, it is desired to develop a resin composition comprisingEVOH, which has good flexibility while still getting the barrierproperties intrinsic to EVOH.

In order to overcome the drawbacks of EVOH, various methods haveheretofore been reported for combining EVOH with ethylenic polymershaving good flexibility. However, most of them are still unsatisfactoryin that the flexibility and drawability of the resin compositionsproduced therein is still poor and that the transparency intrinsic toEVOH is greatly lowered in the resin compositions. At present,therefore, the reported methods have few practical applications in theart. In that situation, it is desired to develop a resin compositionhaving excellent flexibility, drawability and transparency.

EVOH has excellent chemical resistance, oil resistance, stain resistanceand plasticizer shieldability, and EVOH films are much used in interiorfinish work. For example, an EVOH film is laminated on the surface ofinterior material such as wallpaper, decorative plywood, polyvinylchloride leatherette, etc. However, EVOH films have a high degree ofsurface gloss, and are therefore problematic in applications forwallpaper, leatherette and the like that must be matted. In thoseapplications, EVOH films shall be matted by applying thereto mattingrolls under heat and pressure. However, if sufficient pressure could notbe applied thereto, EVOH films could not be well matted. Apart from themethod of using matting rolls for matting films, known are (1) asand-blasting method, (2) a surface-treating method with chemicals, and(3) a method of adding powdery inorganic substances. However, all thosemethods are defective in that they are expensive and their producibilityto form films is poor. In particular, the method (3) of adding powderyinorganic substances is not suitable for EVOH. This is because, if alarge amount of a powdery inorganic substance is added to EVOH so as toattain the intended matting result, the resulting EVOH films will havepin holes and will not able to produce films.

One method of solving this problem is disclosed in JP-A Sho-64-74252,which provides a mat film comprising from 50 to 95% by weight of EVOHand from 5 to 50% by weight of a carboxylic acid-modified polyethyleneresin and in which at least one surface of the mat film provided has adegree of surface gloss of not higher than 60%. However, the blend resincomposition used therein is still unsatisfactory as its thermalstability is poor.

Where multi-layered containers (bottles, cups, etc.) comprising athermoplastic resin and an EVOH resin are produced, the process givesscrap (burs in producing bottles, blanked-off scrap in producing cups,etc.). To recycle the scrap, generally employed is a method ofinterposing a scrap-recycled layer between a thermoplastic resin layerand an EVOH layer of multi-layered containers. In that method, however,where the recycled mixture comprising a thermoplastic resin and an EVOHresin is melt-extruded to form the scrap-recycled layer, its flowstability is often disordered because of the poor compatibility betweenthe EVOH resin and the thermoplastic resin and of the thermaldeterioration of the EVOH resin, often resulting in that themulti-layered sheets having the scrap-recycled layer and the moldingsformed from them through thermoforming will have wavy patterns on theirsurfaces.

In order to solve this problem, a method has been proposed of adding, asa compatibilizer, an EVOH having an ethylene content of from 68 to 98mol % and a degree of saponification of the vinyl acetate component ofat least 20%, to a mixture of an EVOH having an ethylene content of from20 to 65 mol % and a degree of saponification of the vinyl acetatecomponent of at least 96% and a thermoplastic resin (see JP-AHei-3-215032, U.S. Pat. 5,094,921). However, the proposed method is notso much effective enough to completely remove the wavy patterns of themulti-layered sheets and their moldings. Therefore, it is desired todevelop more powerful compatibilizers.

JP-A Hei-4-164941 discloses a polyolefinic resin composition havingexcellent barrier properties, which comprises from 50 to 99.5% by weightof a polyolefin, from 0.4 to 50% by weight of an EVOH, and from 0.1 to15% by weight of a graft polymer having been prepared by grafting apolyolefin with an ethylenic unsaturated carboxylic acid or itsderivative followed by melt-mixing it with apolyamide. JP-AHei-4-164944discloses an EVOH-based resin composition having excellentwaterproofness, excellent gas barrier properties in high-humidityatmospheres, and excellent drawability and flexibility, which comprisesfrom 0.4 to 50% by weight of a polyolefin, from 50 to 99.5% by weight ofan EVOH, and from 0.1 to 15% by weight of the graft polymer noted above.

In those, however, the modified polyolefin to be melt-mixed with apolyamide is one as prepared by grafting a polyolefin with anunsaturated carboxylic acid or its derivative, and this is not a randomcopolymer. Being different from those techniques disclosed, the presentinvention uses a random copolymer. As will be demonstrated inComparative Examples to be mentioned hereinunder, using graft copolymerscould not attain the object of the present invention.

JP-A Hei-8-217934 (European Patent Laid-Open No. 797,625) discloses athermoplastic resin composition comprising from 50 to 85 parts by weightof an EVOH, from 10 to 40 parts by weight of an ionomer of anethylene-unsaturated carboxylic acid copolymer having an unsaturatedcarboxylic acid content of from 4 to 15 mol %, and from 1 to 25 parts byweight of a polyamide. They say that the composition disclosed hasexcellent gas barrier properties, impact resistance, pin-holeresistance, ductility, drawability and transparency. JP-A Hei-9-77945(European Patent Laid-Open No. 797,625) discloses a resin composition asprepared by adding from 0.01 to 3 parts by weight of a metal salt of afatty acid to 100 parts of the resin composition of JP-A Hei-8-217934.They say that the resin composition disclosed has better thermalstability.

However, as will be demonstrated in Comparative Examples to be mentionedhereinunder, the flexibility, especially the bending resistance of thoseresin compositions disclosed is still unsatisfactory even though theycomprise an EVOH as the major component. Nothing is referred to in thoseprior publications relating to a technique of adding a specifichydrophobic thermoplastic resin to the resin compositions comprising thethree components noted above.

Japanese Patent Publication (JP-B) Sho-51-41657 (USP 3,857,754 and3,975,463) discloses a resin composition having excellent processabilityand gas barrier properties, which comprises from 30 to 98 parts byweight of a low-density polyethylene, from 2 to 70 parts by weight of anEVOH, and from 0.5 to 15 parts by weight of at least one thermoplasticpolymer having a carbonyl group in its main chain or side chain andselected from ionomers and polyamides. They say that both an ionomer anda polyamide may be in the composition but are silent at all about thefact that adding the combination of the two to the composition ispreferred and about the effect of the two added in combination. Inaddition, nothing is referred to in the publication relating to themixing ratio of the polyamide and the ionomer to be combined.

In this connection, we, the present inventors have verified that theabsence of any one of a polyamide or an ionomer could not attain theobject of the present invention, as in Comparative Examples to bementioned hereinunder.

In that background noted above, one object of the present invention isto provide a resin composition having excellent compatibility whilehaving excellent barrier properties, mechanical strength, flexibility,drawability, melt stability, heat sealability, coatability, stainresistance and transparency. Another object of the invention is toprovide a resin composition comprising a thermoplastic resin and an EVOHfor multi-layered structures, of which the scrap is well recycled inproducing moldings without making the moldings have wavy patterns ontheir surfaces.

The wording of barrier properties as referred to herein is not limitedto only the concept of so-called gas barrier properties to gases such asoxygen, nitrogen, carbon dioxide and the like, but shall include anyother concepts of non-adsorbability and non-perviousness to flavorcomponents (e.g., limonene, etc.), odor components (e.g., skatole, etc.)and hydrocarbons such as gasoline, etc.

DISCLOSURE OF THE INVENTION

The objects noted above are attained by providing a resin compositioncomprising (A) an ethylene-vinyl alcohol copolymer, (B) a polyamideresin, (C) an ethylene-unsaturated carboxylic acid random copolymer orits metal salt, and (D) a thermoplastic resin except the resins notedabove, of which the solubility parameter (as calculated from the Fedors'formula) is not more than 11, wherein;

the compositional ratio by weight satisfies the following formulae (1)to (4):

0.6≦W(A+D)/W(T)≦0.995  (1)

0.005≦W(B+C)/W(T)≦0.4  (2)

0.01≦W(A)/W(A+D)≦0.99  (3)

0.02≦W(B)/W(B+C)≦0.98  (4)

 wherein;

W(A) indicates the weight of (A) in the composition,

W(B) indicates the weight of (B) in the composition,

W(C) indicates the weight of (C) in the composition,

W(D) indicates the weight of (D) in the composition,

W(T) indicates the total weight of the composition.

Preferably, the resin composition contains from 0.01 to 3 parts byweight, based on the total weight of the composition, of at least oneselected from metal salts of higher aliphatic carboxylic acidsandhydrotalcite compounds. Also preferably, the compositional ratio byweight of W(B)/W(B+C) in the resin composition is not more than 0.5.

In preferred embodiments of the resin composition, the thermoplasticresin (D) forms a matrix phase and the ethylene-vinyl alcohol copolymer(A) forms a dispersed phase; or the ethylene-vinyl alcohol copolymer (A)forms a matrix phase and the thermoplastic resin (D) forms a dispersedphase. In the latter case, it is preferable that the thermoplastic resin(D) has a modulus of elasticity at 20° C. of not more than 500 kg/cm².

One preferred method for producing the resin composition comprisesmixing a polyamide resin (B) and an ethylene-unsaturated carboxylic acidrandom copolymer or its metal salt (C) both in melt followed by mixingthe resulting melt mixture with an ethylene-vinyl alcohol copolymer (A)and a thermoplastic resin (D) all in melt.

Preferred embodiments of using the resin composition of the presentinvention include a multilayered structure comprising at least one layerof the resin composition; a head of a tube container comprising theresin composition; a shaped article comprising the resin composition, ofwhich the surface is painted; a thermoformed container having a layer ofthe resin composition; a flexible film comprising the resin composition;and a mat film comprising the resin composition, of which at least onesurface has a degree of surface gloss of not more than 60%.

Still another preferred embodiment of the present invention is a scraprecycling method of using (B) a polyamide resin and (C) anethylene-unsaturated carboxylic acid random copolymer or its metal saltas the compatibilizer for recycling the scrap of shaped articles thatcomprise, as the major components, (A) an ethylene-vinyl alcoholcopolymer and (D) a thermoplastic resin except the resins noted above,of which the solubility parameter (as calculated from the Fedors'formula) is not more than 11.

In the scrap recycling method, the compatibilizer preferably contains atleast one of metal salts of higher aliphatic carboxylic acids andhydrotalcite compounds.

Still another preferred embodiment of the invention is a multilayeredstructure comprising at least one scrap-recycled layer of the resincomposition as obtained according to the recycling method noted above.

EVOH (A) to be in the composition of the invention is obtained bysaponifying an ethylene-vinyl ester copolymer, and it may have anethylene content of from 15 to 70 mol %, but preferably from 20 to 65mol %, most preferably from 25 to 60 mol %, and a degree ofsaponification of the vinyl ester moiety of at least 85%, but preferablyat least 90%. If the ethylene content of EVOH is smaller than 15 mol %,the melt moldability of the composition is poor, and the water-proofnessand hot water-proofness thereof is also poor. On the other hand, if theethylene content is larger than 70 mol %, the barrier properties of thecomposition are poor. If the degree of saponification of EVOH is smallerthan 85%, the barrier properties and the thermal stability of thecomposition are poor. If the ethylene content is larger than 70 mol % orif the degree of saponification is smaller than 85%, the stainresistance of the film of the composition is poor. If so, in addition,and when the film is laminated on a polyvinyl chloride layer containinga plasticizer to form wallpaper, its ability to prevent the plasticizerfrom bleeding out is poor.

One typical example of vinyl esters to be used for producing EVOH isvinyl acetate, but any other vinyl esters of fatty acids (e.g., vinylpropionate, vinyl pivalate, etc.) are employable herein. If desired,EVOH for use herein may be copolymerized with from 0.0002 to 0.2 mol %of a vinylsilane compound of a comonomer component. The vinylsilanecompound includes, for example, vinyltrimethoxysilane,vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane,γ-methacryloxypropylmethoxysilane. Of those, preferred arevinyltrimethoxysilane and vinyltriethoxysilane. If also desired, EVOHmay be further copolymerized with any other comonomers [e.g., propylene,butylene, unsaturated carboxylic acids and their esters (e.g.,(meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, etc.),vinylpyrrolidone (N-vinylpyrrolidone etc.)] without detracting from theobjects of the invention.

Preferably, EVOH for use in the invention has a melt index (MI, at 190°C. under a load of 2160 g) of from 0.1 to 50 g/10 min., but mostpreferably from 0.5 to 30 g/10 min. For EVOH having a melting point ofaround 190° C. or higher than 190° C., its MI is measured under a loadof 2160 g at different temperatures not lower than its melting point,and the data are plotted on a semi-logarithmic graph where thehorizontal axis indicates the reciprocal of the absolute temperature andthe vertical axis indicates the logarithm of MI, from which isextrapolated the MI of EVOH at 190° C. Those EVOH resins may be usedherein either singly or as combined.

The polyamide resin (B) for use in the invention is a polymer havingamido bonds, which includes, for example, homopolymers such aspolycapramide (nylon-6), polyundecanamide (nylon-11), polylauryl-lactam(nylon-12), polyhexamethylene-adipamide (nylon-6,6),polyhexamethylene-sebacamide (nylon-6,12); as well ascaprolactam/lauryl-lactam copolymer (nylon-6/12),caprolactam/aminoundecanoic acid copolymer (nylon-6/11),caprolactam/ω-aminononanoic acid copolymer (nylon-6/9),caprolactam/hexamethylenediammonium adipate copolymer (nylon-6/6,6),caprolactam/hexamethylenediammonium adipate/hexamethylenediammoniumsebacate copolymer (nylon-6/6,6/6,12), copolymers of adipic acid andmetaxylylenediamine, aromatic nylons such as copolymers ofhexamethylenediamine and m,p-phthalic acids, etc. Those polyamide resinsmay be used herein either singly or as combined.

Of the polyamide resins (B), preferred are those containing a nylon-6component (e.g., nylon-6, nylon-6,12, nylon-6/12, nylon-6/6,6, etc.), inview of their compatibility with EVOH. EVOH and nylon react with eachother to form a gel in the melting step. In order to prevent the thermaldeterioration of the blend composition, it is desirable that the meltingpoint of nylon for use herein is not higher than 240° C., morepreferably not higher than 230° C.

Preferably, the polyamide (B) for use in the invention has a melt index(MI, at 210° C. under a load of 2160 g) of from 0.1 to 50 g/10 min., butmost preferably from 0.5 to 30 g/10 min. For the polyamide (B) having amelting point of around 210° C or higher than 210° C., its MI ismeasured under a load of 2160 g at different temperatures not lower thanits melting point, and the data are plotted on a semi-logarithmic graphwhere the horizontal axis indicates the reciprocal of the absolutetemperature and the vertical axis indicates the logarithm of MI, fromwhich is extrapolated the MI of the polyamide at 210° C.

The ethylene-unsaturated carboxylic acid random copolymer or its metalsalt (C) for use in the invention is a copolymer as obtained throughrandom copolymerization of ethylene and an unsaturated carboxylic acid,or its metal salt as obtained by neutralizing the carboxylic acidcomponent of the copolymer. The latter is a so-called ionomer. For (C),it is extremely important that ethylene and an unsaturated carboxylicacid is random-copolymerized. Using a graft copolymer as obtainedthrough graft copolymerization of ethylene and an unsaturated carboxylicacid in place of the random copolymer could not produce the effects ofthe invention, as is so demonstrated in Comparative Examples to bementioned hereinunder. The reason why the random copolymer or its metalsalt is preferable to the graft copolymer is not clear, but it isbelieved that the reason is because the compatibility of the randomcopolymer with the polyamide resin (B) is better than that of the graftcopolymer with it. In addition, the graft copolymer is unfavorable sincethe carboxyl group existing therein will react with the hydroxyl groupin EVOH to produce gels and fish eyes. The formation of gels and fisheyes is noticeable especially in time-consuming melt-molding. As thecomponent (C) in the resin composition of the invention, preferred isthe ionomer of a metal salt of the ethylene-unsaturated carboxylic acidrandom copolymer to the random copolymer itself, but the reason is notclear. However, it is believed that the reason is because thecompatibility of the ionomer with nylon will be better than that of therandom copolymer itself with it.

The unsaturated carboxylic acid content of the copolymer is preferablyfrom 2 to 15 mol %, but more preferably from 3 to 12 mol %. Theunsaturated carboxylic acid includes, for example, acrylic acid,methacrylic acid, ethacrylic acid, maleic acid, monomethyl maleate,monoethyl maleate, maleic anhydride, etc. Especially preferred areacrylic acid and methacrylic acid. The copolymer may contain any othercomonomers. The additional comonomers include, for example, vinyl esterssuch as vinyl acetate, vinyl propionate; unsaturated carboxylates suchas methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutylacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,isobutyl methacrylate, diethyl maleate; carbon monoxide, etc.

The metal ion that constitutes the ionomer includes, for example, alkalimetals such as lithium, sodium, potassium, etc.; zinc; alkaline earthmetals such as magnesium, calcium, etc. Especially preferred is zinc, asthe compatibility of zinc ionomers with nylon is good. It is desirablethat the degree of neutralization of the ionomer is at most 100%, butmore preferably at most 90%, even more preferably at most 70%. Thelowermost limit of the degree of neutralization may be generally atleast 5%, but preferably at least 10%, more preferably at least 30%.

Preferably, the ethylene-unsaturated carboxylic acid random copolymer orits metal salt for use in the invention has a melt index (MI, at 190° C.under a load of 2160 g) of from 0.05 to 50 g/10 min., but mostpreferably from 0. 5 to 30 g/10 min. Those ethylene-unsaturatedcarboxylic acid random copolymers and their metal salts may be usedherein either singly or as combined.

The thermoplastic resin (D) for use in the invention shall differ fromthe other components (A), (B) and (C), and its solubility parameter mustbe at most 11. Specifically, the solubility parameter (as calculatedfrom the Fedors' formula) of the thermoplastic resin (D) is near to thatof the ethylene-unsaturated carboxylic acid random copolymer or its salt(C), and therefore the compatibility of the four components (A), (B),(C) and (D) with each other is high. If, the solubility parameter of thethermoplastic resin (D) is more than 11, the compatibility of the fourcomponents (A), (B), (C) and (D) with each other is low. If so, thescrap recyclability, the thermoformability, the mechanical strength andthe transparency of the blend resin composition will be greatly lowered.

The thermoplastic resin (D) having a solubility parameter of at most 11includes, for example, polyolefinic resins, styrenic resins, polyvinylchloride-based resins, etc. Of those, most preferred are polyolefinicresins. Examples of the polyolefinic resins include α-olefinichomopolymers such as high-density or low-density polyethylene,polypropylene, polybutene-1, etc.; copolymers of α-olefins selected fromethylene, propylene, butene-1, hexene-1, etc.; and also copolymers ofsuch α-olefins with any other comonomers. The comonomers to becopolymerized with α-olefins include, for example, diolefins; vinylcompounds such as vinyl chloride, vinyl acetate, etc.; unsaturatedcarboxylic acids such as maleic acid, acrylic acid, methacrylic acid,etc.; and their anhydrides. Examples of the styrenic resins includepolystyrenes, acrylonitrile-butadiene-styrene copolymer resins (ABS),acrylonitrile-styrene copolymer resins (AS), etc. Those thermoplasticresins may be used herein either singly or as combined.

Preferably, the thermoplastic resin (D) for use in the invention has amelt index (MI, at 190° C. under a load of 2160 g) of from 0.05 to 100g/10 min., but more preferably from 0.05 to 50 g/10 min., mostpreferably from 0.5 to 30 g/10 min. For the resin (D) having a meltingpoint of around 190° C. or higher than 190° C., its MI is measured undera load of 2160 g at different temperatures not lower than its meltingpoint, and the data are plotted on a semi-logarithmic graph where thehorizontal axis indicates the reciprocal of the absolute temperature andthe vertical axis indicates the logarithm of MI, from which isextrapolated the MI of the resin (D) at 190°C.

The most characteristic feature of the present invention is that acombination of the two components of the polyamide (B) and theethylene-unsaturated carboxylic acid random copolymer or its metal salt(C) is used as the compatibilizer for compatibilizing the EVOH (A) andthe thermoplastic resin (D), and the combination of the polyamide (B)and the ethylene-unsaturated carboxylic acid random copolymer or itsmetal salt (C) significantly improves the compatibility between the EVOH(A) and the thermoplastic resin (D), thereby producing the resincomposition having excellent characteristics. In other words, as themeans of improving the compatibility between the EVOH (A) and thethermoplastic resin (D) which are poorly compatible with each other asgreatly differing in the solubility parameter, we, the inventors haveused, as a compatibilizer for both (A) and (D), the combination of thepolyamide (B) and the ethylene-unsaturated carboxylic acid randomcopolymer or its metal salt (C), the former (B) being highly compatiblewith the EVOH (A) while the latter (C) being highly compatible with thethermoplastic resin (D), and have found the resin composition of thepresent invention.

The compositional ratio by weight of the components constituting theresin composition of the invention satisfies the following formulae (1)to (4):

0.6≦W(A+D)/W(T)≦0.995  (1)

0.005≦W(B+C)/W(T)≦0.4  (2)

 0.01≦W(A)/W(A+D)≦0.99  (3)

0.02≦W(B)/W(B+C)≦0.98  (4)

wherein;

W(A) indicates the weight of (A) in the composition,

W(B) indicates the weight of (B) in the composition,

W(C) indicates the weight of (C) in the composition,

W(D) indicates the weight of (D) in the composition,

W(T) indicates the total weight of the composition.

Preferably, the formulae (1) to (4) are the following:

0.65≦W(A+D)/W(T)≦0.99  (1′)

0.01≦W(B+C)/W(T)≦0.35  (2′)

0.02≦W(A)/W(A+D)≦0.98  (3′)

0.04≦W(B)/W(B+C)≦0.96  (4′)

More preferably, they are the following:

0.70≦W(A+D)/W(T)≦0.985  (1″)

0.015≦W(B+C)/W(T)≦0.30  (2″)

0.03≦W(A)/W(A+D)≦0.97  (3″)

0.05≦W(B)/W(B+C)≦0.95  (4″)

If W(A+D)/W(T) is more than 0.995, or if W(B+C)/W(T) is less than 0.005,the compatibility between the EVOH (A) and the thermoplastic resin (D)is poor, and the effects of the invention could not be attained. IfW(A+D)/W(T) is less than 0.6, or if W(B+C)/W(T) is more than 0.4, theproportions of the EVOH (A) and the thermoplastic resin (B) to the totalamount of the composition are lowered, resulting in that the barrierproperties intrinsic to the EVOH (A) and the melt moldability intrinsicto the thermoplastic resin (D) of the composition are not good.

If W(A)/W(A+D) is less than 0.01, the gas barrier properties of thecompositions are not good; but if W(A)/W(A+D) is more than 0.99, theflexibility of the composition could not be satisfactorily improved.

If W(B)/W(B+C) is less than 0.02, the compatibility between the EVOH (A)and the polyamide resin (B) is low; but if W(B)/W(B+C) is more than0.98, the compatibility between the ethylene-unsaturated carboxylic acidrandom copolymer or its metal salt (C) and the thermoplastic resin (D)is poor.

Poor compatibility between the constituent components brings about thereduction in the mechanical strength of the resin composition itself andeven the reduction in the barrier properties, the heat sealability, thecoatability, the mattability, the flexibility and the drawability of thecomposition. In addition, when the scrap in a process of producingmulti-layered containers comprising thermoplastic resin and EVOH isrecycled to produce multi-layered sheets and their thermoformed articlescomprising the scrap-recycled layer, the sheets and the articlesproduced will have wavy patterns on their surfaces if the compatibilitybetween the two components, thermoplastic resin and EVOH used is poor.

Preferably, the compositional ratio by weight of the polyamide resin (B)and the ethylene-unsaturated carboxylic acid random copolymer or itsmetal salt (C), W(B)/W(B+C) is at most 0.5, but more preferably at most0.45, most preferably at most 0.4, in view of the thermal stability ofthe composition. Defining the compositional ratio by weight ofW(B)/W(B+C) to the range noted above further improves the melt stabilityof the resin composition, resulting in that the composition is formedinto articles with better outward appearance even in time-consuming meltmolding. In that condition, therefore, the producibility of articlesfrom the composition is improved, but the reason is not clear. However,it is believed that the reason is because the reaction between EVOH andpolyamide will have some negative influences on the melt stability ofthe composition.

Where the constituent resins are formulated into the composition at thecompositional ratio noted above, their dispersed conditions are notspecifically defined. Depending on the use of the composition, however,it is desirable that the thermoplastic resin (D) forms a matrix phasewhile the EVOH (A) forms a dispersed phase in some cases; but, on thecontrary, it is desirable that the EVOH (A) forms a matrix phase whilethe thermoplastic resin (D) forms a dispersed phase in some other cases.

The resin composition in which the thermoplastic resin (D) forms amatrix phase and the EVOH (A) forms a dispersed phase is advantageous inthat it keeps the characteristics of the thermoplastic resin as a wholewhile additionally having the characteristics of EVOH added thereto.Accordingly, the resin composition of that type is favorable for headsof tube containers, as the heads comprising it shall get improvedbarrier properties while still having good heat sealability andmechanical strength; and it is also favorable for articles, as thearticles comprising it shall have improved coatability while stillgetting good mechanical strength. In addition, the scrap of the resincomposition of that type is w ell recycled for various applications, ascomprising the thermoplastic resin as the major component and EVOH asthe minor component.

The resin composition having the dispersed condition of that type may beobtained by reducing the ratio of W(A)/W(A+D), or by using (A) having alarger melt viscosity than (D).

In the resin composition of that type, the ratio of W(A)/W(A+D) ispreferably at most 0.65, but more preferably at most 0.6. If the ratioof W(A)/W(A+D) is more than 0.65, the thermoplastic resin could hardlyform a matrix phase.

As opposed to that, the resin composition in which the EVOH (A) forms amatrix phase and the thermoplastic resin (D) forms a dispersed phase isadvantageous in that it keeps the excellent characteristics of EVOH as awhole while additionally having the characteristics of the thermoplasticresin added thereto. Accordingly, the resin composition of this type isfavorable for films, as the films comprising it shall get improvedflexibility and drawability while still having the excellent barrierproperties intrinsic to EVOH; and it is also favorable for mat films, asthe mat films comprising it shall get a lowered degree of surface glosswhile still having the excellent stain resistance intrinsic to EVOH.

The resin composition having the dispersed condition of this type may beobtained by increasing the ratio of W(A)/W(A+D), or by using (A) havinga smaller melt viscosity than (D).

In the resin composition of this type, the ratio of W(A)/W(A+D) ispreferably at least 0.65, but more preferably at least 0.7. If the ratioof W(A)/W(A+D) is less than 0.65, EVOH in the composition could hardlyform a matrix phase.

In the resin composition where the EVOH (A) forms a matrix phase and thethermoplastic resin (D) forms a dispersed phase, it is preferable thatthe thermoplastic resin (D) has a modulus of elasticity (ASTM D882) at20° C. of at most 500 kg/cm², but more preferably at most 400 kg/cm²,even more preferably at most 300 kg/cm².

EVOH is highly rigid but is poorly flexible, as compared with any otherordinary polymers, and is not resistant to bending. Therefore, it couldnot be used in flexible packaging applications. When EVOH is processedin a process comprising a drawing step for producing skin-packwrappings, shrink wrappings, thermoformed films or sheets and the like,the thickness of the thermoformed articles is often uneven due to unevendrawing, resulting in that the gas barrier properties and even theoutward appearance of the articles are poor. Therefore, in order torealize good bending resistance and drawability, desired is acomposition having a lower Young's modulus and capable of being drawn bysmaller force. To satisfy this requirement, adding the thermoplasticresin (D) to the EVOH (A) is effective. In particular, using thethermoplastic resin (D) having a modulus of elasticity at 20° C. of atmost 500 kg/cm² is especially effective.

Examples of the thermoplastic resin (D) having a modulus of elasticityof at most 500 kg/cm² include very-low-density polyethylene (VLDPE),ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylatecopolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA),ethylene-propylene copolymer (EPR), styrenic elastomers (SEBS resins,etc.), etc.

The resin composition of the invention may optionally contain at leastone of metal salts of higher aliphatic carboxylic acids and hydrotalcitecompounds, in which the additional component prevents the reaction ofthe EVOH (A) with the polyamide resin (B) that may cause the thermaldeterioration of the EVOH (A). In addition, as will be known fromExamples to be mentioned hereinunder, multi-layered, co-extruded sheetsthat comprise a scrap-recycled layer of the composition are good, ashaving no wavy patterns on their surfaces.

As examples of the hydrotalcite compounds, mentioned are composite saltsof M_(x)Al_(y)(OH)2x+3y-2z(A)z.aH₂O (where M represents Mg, Ca or Zn; Arepresents CO₃ or HPO₄; and x, y, z and a each are a positive number).Especially preferred examples of those compounds are mentioned below.

Mg₆Al₂(OH)₁₆CO₃.4H₂O

Mg₈Al₂(OH)₂₀CO₃.5H₂O

Mg₅Al₂(OH)₁₄CO₃.4H₂O

Mg₁₀Al₂(OH)₂₂(CO₃)₂.4H₂O

Mg₆Al₂(OH)₁₆HPO₄.4H₂O

Ca₆Al₂(OH)₁₆CO₃.4H₂O

Zn₆Al₆(OH)₁₆CO₃.4H₂O

Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O

As the hydrotalcite compound, also employable herein is a hydrotalcitesolid solution of[Mg_(0.75)Zn_(0.25)]_(0.67)Al_(0.33)(OH)₂(CO₃)_(0.167).0.45H₂O such asthat disclosed in JP-A Hei-1-308439 (U.S. Pat. No. 4,954,557).

The metal salts of higher aliphatic carboxylic acids are metal salts ofhigher fatty acids having from 8 to 22 carbon atoms. The higher fattyacids having from 8 to 22 carbon atoms include lauric acid, stearicacid, myristic acid, etc.; and the metals include sodium, potassium,magnesium, calcium, zinc, barium, aluminium, etc. Of those, preferredare alkaline earth metals such as magnesium, calcium, barium, etc.

The content of the metal salts of higher aliphatic carboxylic acids andhydrotalcite compounds is preferably from 0.01 to 3 parts by weight,more preferably from 0.05 to 2.5 parts by weight, based on the totalweight of the resin composition. The resin composition of the inventionmay optionally contain any other additives (heat stabilizers,plasticizers, UV absorbents, antioxidants, colorants, fillers, otherresins, etc.), without detracting from the objects of the invention.

The composition of the invention can be produced easily by melt-kneadingthe constituent components in any ordinary melt-kneading device. Theblending method for producing the composition is not specificallydefined. For example, employable is a method comprising pelletizing theEVOH (A), the polyamide (B), the ethylene-unsaturated carboxylic acidrandom copolymer or its metal salt (C) and the thermoplastic resin (D)all at a time through a single-screw or twin-screw extruder and dryingthe resulting pellets; or a method comprising melt-mixing, cooling andpelletizing the polyamide resin (B) and the ethylene-unsaturatedcarboxylic acid random copolymer or its metal salt (C), followed bydry-blending the resulting pellets with the EVOH (A) and thethermoplastic resin (D), then pelletizing the resulting mixture througha single-screw or twin-screw extruder and further drying the resultingpellets.

Above all, as will be demonstrated in Examples to be mentionedhereinunder, preferred is a method comprising melt-blending thepolyamide resin (B) and the ethylene-unsaturated carboxylic acid randomcopolymer or its metal salt (C) followed by melt-blending the resultingmelt with the EVOH (A) and the thermoplastic resin (D), as the methodeffectively attains the objects of the invention. Though not clear, itis believed that the reason is because the previously prepared blend ofthe polyamide resin (B) and the ethylene-unsaturated carboxylic acidrandom copolymer or its metal salt (C), which acts as the compatibilizerfor the EVOH (A) and the thermoplastic resin (D), will effectivelyimproves the compatibility between the EVOH (A) and the thermoplasticresin (D) to give the four-component composition having stablemorphology.

In the melt-blending operation, the blend formed will be uneven or willproduce and have gels and agglomerates. Therefore, it is desirable thatthe blending and pelletization is effected by the use of a powerfulextruder capable of blending the components in a high degree, while thehopper mouth is sealed with nitrogen gas, and that the extrusion iseffected at low temperatures.

The resin composition of the invention that comprises the EVOH (A), thepolyamide resin (B), the ethylene-unsaturated carboxylic acid randomcopolymer or its metal salt (C) and the thermoplastic resin (D) may beformed into single-layered articles, but may also be formed intotwo-layered or more multi-layered articles along with other varioussubstrates. In the multi-layered articles, a thermoplastic resin layermay be adjacent to the layer of the composition of the invention. Aspreferred examples of the thermoplastic resin for the layer, mentionedare polyolefins, such as high-density, middle-density or low-densitypolyethylene; polyethylene copolymerized with vinyl acetate, acrylatesor α-olefins such as butene, hexene, etc.; ionomer resins; polypropylenehomopolymer; polypropylene copolymerized with α-olefins such asethylene, butene, hexene, etc.; modified polypropylene blended withrubber polymers; as well as thermoplastic resins as prepared by addingmaleic anhydride to those resins through mere addition or grafting. Forthe other thermoplastic resin layers in those, mentioned are polyamideresins, polyester resins, polystyrene resins, polyvinyl chloride resins,acrylic resins, polyurethane resins, polycarbonate resins, polyvinylacetate resins, etc.

If desired, an adhesive resin layer may be interposed between the layerof the composition of the invention and the adjacent thermoplastic resinlayer. The adhesive resin for the layer is not specifically defined, buttypically includes olefinic polymers or copolymers (e.g., LLDPE, VLDPE,etc.), ethylene-vinyl acetate copolymers or ethylene-(meth)acrylatecopolymers as grafted with unsaturated carboxylic acids or theiranhydrides (maleic anhydride, etc.).

The method for producing the multi-layered structures is notspecifically defined. For producing them, for example, employable is anytechnique of extrusion lamination, dry lamination, extrusionblow-molding, co-extrusion lamination, co-extrusion sheeting,co-extrusion pipe forming, co-extrusion blow-molding, co-extrusioninjection-molding, solution coating, etc. If desired, the laminates thusproduced may be re-heated at temperatures not higher than the meltingpoint of EVOH and subjected to secondary processing of, for example,vacuum or pressure deep-drawing, blow molding or the like.

The layer constitution of the multi-layered structures is notspecifically defined. However, taking the moldability and the productioncosts into consideration, preferred are thermoplastic resin layer/resincomposition layer/thermoplastic resin layer; resin compositionlayer/adhesive resin layer/thermoplastic resin layer; thermoplasticresin layer/adhesive resin layer/resin composition layer/adhesive resinlayer/thermoplastic resin layer. Where thermoplastic resin layers areprovided as the both outer layers, the resins for those layers maydiffer or may be the same. The scrap as collected in the process ofextrusion molding, blow molding or thermoforming may be recycled in thethermoplastic resin layer by blending it with the resin for the layer,or may be used to form a separate recycled layer.

The resin composition of the invention may be formed into articleshaving excellent barrier properties, mechanical strength, flexibility,drawability, melt stability, scrap recyclability, heat sealability,coatability, stain resistance and transparency, and it has manyapplications in various fields.

For example, the resin composition in which the thermoplastic resin (D)forms a matrix phase and the EVOH (A) forms a dispersed phase may beformed into single-layered barriers having excellent barrier properties,for example, as heads of two-piece tube containers, small-sized,single-layered barrier containers (bottles, cups, etc.), papercontainers, barrier spouts for bag-in boxes, etc. In addition, it isuseful for car parts of plastics with improved coatability, as well asfor daily necessities of plastics or plastic parts of electricappliances for household use with stain resistance, etc. Moreover, it isfurther useful for fuel tanks or fuel tubes having barrier properties toorganic solvents.

One embodiment of using the resin composition, in which thethermoplastic resin (D) forms a matrix phase and the EVOH (A) forms adispersed phase, for producing a head of a two-piece tube container isdescribed. To this use, the resin composition of the invention isfavorable, as it improves the barrier properties of the head formedwhile still having excellent heat sealability and mechanical strength.

In this embodiment, the thermoplastic resin (D) to be used is preferablypolyolefin, most preferably polyethylene, in view of the mechanicalstrength of the head formed and the heat sealability thereof to the tubebody.

The compositional ratio by weight of the thermoplastic resin (D) and theEVOH (A), W(A)/W(A+D) is preferably at least 0.2, more preferably atleast 0.3, most preferably at least 0.4, in order to ensure good barrierproperties of the head.

Another embodiment of using the resin composition, in which thethermoplastic resin (D) forms a matrix phase and the EVOH (A) forms adispersed phase, for producing a shaped article to be painted isdescribed. To this use, the resin composition of the invention isfavorable, as the paint-coatability of the article formed is good, andnaturally the mechanical strength thereof is also good.

In this embodiment, the thermoplastic resin (D) to be used is preferablypolyolefin, most preferably polypropylene, in view of the mechanicalstrength, the stiffness and the impact resistance of the article formed.

Also preferably, the EVOH (A) to be used has an ethylene content of atmost 50 mol %, more preferably at most 45 mol %, most preferably at most40 mol %, in view of the coatability of the article formed. The degreeof saponification of the EVOH (A) to be used is preferably at least 90%,more preferably from 92 to 98%, most preferably from 93 to 97%.

The compositional ratio by weight of the thermoplastic resin (D) and theEVOH (A), W(A)/W(A+D) is preferably at most 0.3, more preferably at most0.2, most preferably at most 0.15, in view of the mechanical strength,the stiffness and the impact resistance of the thermoplastic resin (D)and of the economical efficiency of the composition. For the samereason, the compositional ratio by weight of the sum of the polyamideresin (B) and the ethylene-unsaturated carboxylic acid random copolymeror its metal salt (C) to the total weight of the resin composition,W(B+C)/W(T) is preferably at most 0.15, more preferably at most 0.1.

On the other hand, the resin composition, in which the EVOH (A) forms amatrix phase and the thermoplastic resin (D) forms a dispersed phase,gets excellent flexibility, drawability and transparency to EVOH, and istherefore useful for flexible films, bag-in boxes that requires goodbending resistance, and skin-pack wrappings, shrink wrappings,thermoformed containers and the like that require good drawability andthermoformability.

In addition, films of the resin composition, in which the EVOH (A) formsa matrix phase and the thermoplastic resin (D) forms a dispersed phase,may have a reduced degree of surface gloss while still getting theexcellent stain resistance intrinsic to EVOH, and therefore, they areuseful as mat films.

The thermoplastic resin (D) for such mat films is preferably polyolefin,more preferably polyethylene, in view of the mechanical strength and theeconomical efficiency of the films. The polyethylene for that use ispreferably a resin having an ethylene content of at least 60 mol %. Thecomonomers which the resin, polyethylene may have in a ratio of lessthan 40 mol % include, for example, olefins such as propylene, butylene,etc.; dienes such as isoprene, butadiene, etc.; styrene and itsderivatives; various acrylates, various methacrylates, vinyl acetate,etc. Apart from those, the resin, polyethylene may further have anyother comonomers in a ratio of at most 1 mol %. The additionalcomonomers include, for example, α,β-unsaturated fatty acids and theiranhydrides such as maleic anhydride, etc.; and compounds having variousfunctional groups such as methacrylic acid glycidyl ether, ethyleneoxide, propylene oxide, etc. In particular, polyethylene resinscopolymerized or grafted with from 0.0005 to 0.5 mol % of any ofα,β-unsaturated fatty acids and their anhydrides are especiallyfavorably used in the invention.

In the resin composition for mat films, the amount of the thermoplasticresin (D) is preferably from 4 to 45% by weight, more preferably from 10to 30% by weight, based on the total weight of the components (A), (B),(C) and (D), in order to more effectively exhibit the effects. If theresin (D) content is less than 4% by weight, the mat films could nothave a satisfactorily reduced degree of surface gloss. On the otherhand, if the resin (D) content is more than 45% by weight, themorphology of the composition will vary, often resulting in that the matfilms could not have the characteristics intrinsic to EVOH films.

In the resin composition for mat films, the ratio by weight of thepolyamide resin (D) to the ethylene-unsaturated carboxylic acid randomcopolymer or its metal salt (C) is from 2/98 to 70/30, but preferablyfrom 3/97 to 60/40, most preferably from 5/95 to 50/50. If the ratio ofthe polyamide resin is less than 2%, the dispersibility of thecomposition will be poor, resulting in that not only the degree ofsurface gloss of the mat films formed could not be satisfactorilyreduced but also the mechanical characteristics thereof will be poor.If, however, the ratio of the polyamide resin is more than 70%, EVOH andnylon in the composition will react too greatly with each other,resulting in that the producibility of mat films from the compositionwill be lowered.

In the resin composition for mat films, the sum of the polyamide resin(B) and the ethylene-unsaturated carboxylic acid random copolymer or itsmetal salt (C) based on the total amount of the components (A), (B), (C)and (D) is from 1 to 20% by weight, but preferably from 2 to 15% byweight, most preferably from 3 to 10% by weight. If the sum of (B) and(C) is less than 1% by weight, the dispersibility of the components (A)and (B) in the composition will be poor, resulting in that not only thedegree of surface gloss of the mat films formed could not besatisfactorily reduced but also the mechanical characteristics thereofwill be poor. If, however, the sum of (B) and (C) is more than 20% byweight, the dispersibility of the thermoplastic resin (D) in thecomposition will be too great, resulting in that the degree of surfacegloss of the mat films formed could not be satisfactorily reduced.

It is important that at least one surface of the mat films formed fromthe resin composition of the invention shall have a degree of surfacegloss of at most 60%, but preferably at most 50%, most preferably atmost 40%. Films having a degree of surface gloss of more than 60% couldno more be mat films. The degree of surface gloss as referred to hereinis a mean value of the data off non-defined five points of one sample asmeasured with a Murakami's surface gloss meter.

The thickness of the mat films is not specifically defined, butpreferably falls between 10 and 50 μm. Thick films having a thickness ofmore than 50 μm are too rigid, and when they are laminated on substratesof interior materials such as cellulosic wallpaper, polyvinylchloride-based plastic wallpaper and the like, the patterns capable ofbeing formed on their surfaces will be limited.

Laminating the mat films of the invention on substrates of interiormaterials such as wall paper, decorative plywood and the like producesvarious good results. For example, the mat films prevent plasticizer andother unfavorable substances from bleeding out; they improve the stainresistance of the laminates to various contaminants; and the laminatesthus having non-glossy appearance get a high-quality feel. Laminatingthe mat films on leather or leatherette produces the same good results.

Still another preferred embodiment of the invention is a scrap recyclingmethod of using a combination of (B) a polyamide and (C:) anethylene-unsaturated carboxylic acid random copolymer or its metal saltas the compatibilizer for recycling the scrap of shaped articles thatcomprise, as the major components, (A) an EVOH and (D) a thermoplasticresin, especially the scrap of multi-layered articles comprising a layerof (A) and a layer of (D). The shaped articles comprising, as the majorcomponents, (A) an EVOH and (D) a thermoplastic resin as referred toherein indicate those in which the sum of (A) and (D) is at least a halfof the total weight of the article.

Where the scrap in the process of extrusion molding, blow molding,thermoforming or the like for producing shaped articles comprising (A)an EVOH and (D) a thermoplastic resin is recycled as a separate recycledlayer in multi-layered sheets or other thermoformed articles, the sheetsand articles having the separate recycled layer often have wavy patternson their surfaces owing to the poor compatibility between the EVOH (A)and the thermoplastic resin (D). Adding the polyamide (B) and theethylene-unsaturated carboxylic acid random copolymer or its salt (C) tothe molding composition comprising (A) and (D) significantly overcomesthe problem of such wavy patterns. Along with the components (B) and(C), adding to the molding composition at least one of metal salts ofhigher aliphatic carboxylic acids and hydrotalcite compounds furtheraugments the effect of the components (B) and (C). Preferably, theamount of the additional component of metal salts of higher aliphaticcarboxylic acids and hydrotalcite compounds may be from 0.1 to 50 partsby weight based on the sum of (B)+(C).

The thus-recycled resin composition is effectively used in multi-layeredstructures having at least one scrap-recycled layer. For example,multi-layered sheets for thermoforming that comprise the scrap-recycledlayer can be thermoformed into containers with good outward appearance.In particular, preferred are multi-layered structures having at leastone EVOH layer in addition to the scrap-recycled layer, as they get goodbarrier properties.

For recycling the scrap of multi-layered structures, employable areother different methods apart from the method noted above that comprisesadding the polyamide resin (B) and the ethylene-unsaturated carboxylicacid random copolymer or its metal salt (C) directly to the scrap. Forexample, the components (B) and (C) may be previously blended with thecomposition for any one layer of multi-layered structures; or they mayform at least one layer of multi-layered structures, for example, anadhesive layer between the layers of EVOH and polyolefin ofmulti-layered structures.

The thermoplastic resin (D) to be in the recycled composition is notspecifically defined, but preferred is polypropylene in view of themechanical strength, the impact resistance, the secondary processabilityand the economical efficiency of the composition. Also preferred ispolystyrene in view of the stiffness, the surface gloss, the secondaryprocessability and the economical efficiency of the composition.

In the composition, the compositional ratio by weight of thethermoplastic resin (D) and the EVOH (A), W(A)/W(A+D) is preferably atmost 0.3, more preferably at most 0.25, most preferably at most 0.2, inview of the mechanical strength, the stiffness and the impact resistanceof the thermoplastic resin (D) and of the economical efficiency of thecomposition. For the same reason, the compositional ratio by weight ofthe sum of the polyamide resin (B) and the ethylene-unsaturatedcarboxylic acid random copolymer or its metal salt (C) to the totalweight of the resin composition, W(B+C)/W(T) is preferably at most 0.15,more preferably at most 0.1, most preferably at most 0.08.

As has been mentioned hereinabove, the resin composition of the presentinvention has excellent barrier properties, mechanical strength,flexibility, drawability, melt stability, scrap-recyclability, heatsealability, coatability, stain resistance and transparency, and hasmany applications in various fields.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic side view partly in section of a tube container ofone embodiment of the invention.

FIG. 2 is an enlarged view of the cross-section of the tube container ofFIG. 1.

The numeral references in FIG. 1 and FIG. 2 are as follows:

1 Cylindrical Body

2 Head

2 a Male Screw

2 b Shoulder

3 Shoulder of Head

4 Heat-sealed Bottom

5 Heat-seal Layer (LDPE)

6 Adhesive Resin

7 Barrier Resin EVOH

8 Adhesive Resin

9 Outer Layer (LDPE)

BEST MODES OF CARRYING OUT THE INVENTION

Now, the invention is described in more detail with reference to thefollowing Examples, which, however, are not intended to restrict thescope of the invention.

Of the following Examples, resin materials shown in Tables 1 to 4 wereused in <Examples of Head of Two-piece Tube Container>, <Examples forCoatability>, <Examples for Scrap Recyclability>and <Examples ofFlexible Film>. Table 1 shows examples of EVOH (A); Table 2 shows thoseof polyamide resin (B); Table 3 shows those of ethylenic copolymer resin(C); and Table 4 shows those of thermoplastic resin (D).

TABLE 1 Ethylene-Vinyl Alcohol Copolymers Degree of Ethylene Contentsaponification Melting Point MFR^(*1)) (mol%) (mol%) (° C.) (g/10 min.)A-1 27 99.7 191 6^(*2)) A-2 32 99.5 183 1.6 A-3 44 99.5 165 6 A-4 4899.6 160 15 A-5 32 96.5 170 10 ^(*1))Condition for measurement: 190°C.-2160 g ^(*2))Condition for measurement: 210° C.-2160 g

TABLE 2 Polyamide Resins Copolymeri- zation Ratio of 6- PA/12-PA MeltingPoint Name of Resin (mol%) (° C.) Trade Name B-1 6-Polyamide 100/0  225Ube Nylon 1011FB B-2 6/12-Polyamide 80/20 200 Ube Nylon 7024B

TABLE 3 Ethylenic Copolymer Resins MFR *1) Density Melting Point Type ofResin (g/10 min) (g/cc) (° C.) Remarks C-1 Ethylene-Methacrylic AcidRandom Copolymer (EMAA) 7 0.94  98 *2) C-2 Ethylene-Methacrylic AcidRandom Copolymer 10  0.94  95 *3) (Ionomer) C-3 Maleic Anhydride-GraftedModified Polyethylene 3 0.91 120 *4) C-4 Partially-saponifiedEthylene-Vinyl Acetate Copolymer 5 0.97 110 *5) *1) Condition formeasurement: 190° C. - 2160 g *2) Degree of copolymerization withmethacrylic acid: 4.3 mol % *3) Degree of copolymerization withmethacrylic acid: 7.5 mol % Degree of neutralization: 40%, Metal forneutralization: zinc *4) Maleic anhydride content: 2.1 wt. % *5)Ethylene Content: 89 mol %, Degree of saponification: 97%

TABLE 4 Thermoplastic Resins Modulus of Type of Resin SolubilityElasticity Melting Point MFR *3) *1) Parameter (kg/cm²) *2) (° C.) (g/10min) Trade Name D-1 HDPE 8.6 3700  128 5 Showa Denko; HD-5050 D-2 LDPE8.6 600 110 2 Mitsui Chemical; Misolan 9725 D-3 PP 8.0 — 165  15 *4)Ube; Polypropylene J130G D-4 PP 8.0 — 165 1.2 *4) Mitsubishi; NoblenEA7A D-5 PS 10.6 — —   3 *5) Idemitsu; Styrol ET-61 D-6 VLDPE 8.5 260 98   9.5 Dow Chemical; Affinity FW1650 D-7 PET 11.5 — 252 — Kuraray;KS750RCT D-8 EVA 9.2  90  72 6 Mitsui Dupont; EVAFLEX EV260 D-9 PU 11.6120 — — Kuraray; Kuramilon 2190 *1) HDPE: High-density polyethyleneLDPE: Low-density polyethylene PP: Polypropylene PS: Polystyrene VLDPE:Very-low-density polyethylene (ethylene-1-octene copolymer) PET:Polyethylene terephthalate EVA: Ethylene-vinyl acetate copolymer (vinylacetate content: 28 wt. %) PU: Polyurethane (ester-type polyurethane)*2) Condition for measurement: ASTM D822 *3) Condition for measurement:190° C. - 2160 g *4) Condition for measurement: 230° C. - 2160 g *5)Condition for measurement: 200° C. - 2160 g

EXAMPLES OF HEAD OF TWO-PIECE TUBE CONTAINER Example 1-1

Of the resins shown in Tables 1 to 4, a blend comprised of 40 parts byweight of EVOH (A-3), 5 parts by weight of polyamide (B-2), 15 parts byweight of ethylene-methacrylic acid random copolymer (EMAA; C-1) and 40parts by weight of high-density polyethylene (HDPE; D-1) was preparedaccording to the method mentioned below. Precisely, polyamide (B-2) andEMAA (C-1) were fed into a vent-type, twin-screw extruder, andpelletized through it at 220° C. in the presence of nitrogen. Theresulting blend pellets were further blended with EVOH (A-3) and HDPE(D-1), in the same manner as above, to obtain the intended resincomposition pellets.

Next, using the tube container-molding machine for injection moldingdisclosed in JP-A Sho-56-25411 (JP-B Sho-64-7850), the resin compositionpellets were molded into tube containers. In this process, the resincomposition pellets were fed into the injection-molding machine, while acylindrical tube which had been previously formed for bodies of thecontainers was fed into the mold of the machine.

The injection-molding machine used herein is a 35 mmφ in-line screw-typeinjection-molding machine, in which were formed the heads of the tubecontainers at a cylinder temperature of 240° C. and at a nozzletemperature of 235° C. The tube containers thus formed herein had anouter diameter of 35 mmφ, outer and inner diameters of the mouth of 12mmφ and 7 mmφ, respectively, and a wall thickness of the head of 2 mm.The cylindrical tube for the bodies was prepared through co-extrusionusing a ring die, and had a multi-layered structure of low-densitypolyethylene (LDPE, Mitsui Petro-chemical's Ultzex 3520L, having athickness of 150 μ)/adhesive resin (Mitsui Petro-chemical's Admer NF500,having a thickness of 20 μ)/EVOH (B-l,having a thickness of 20μ)/adhesive resin(Mitsui Petro-Chemical's Admer NF500, having athickness of 20 μ)/LDPE (Mitsui Petro-chemical's Ultzex 3520L, having athickness of 150 μ).

Observing the head formed herein with an electronic microscope verifiedthat HDPE (D-1) formed a matrix phase and EVOH (A-3) formed a dispersedphase in the head.

The tube containers obtained herein were tested for the contentspreservability, the heat sealability, the mechanical strength of thehead, and the outward appearance of the head, according to the methodsmentioned below. To determine the barrier strength of the head itself,the resin pellets for the head were formed into a film, and the oxygentransmission rate (OTR) -through the film was measured. The resultsobtained are shown in Table 5.

(1) Oxygen Transmission Rate (OTR):

A resin composition sample was melt-extruded through a T-die at 235° C.into a film having a thickness of 100μ. The oxygen transmission ratethrough the film was measured at 20° C. and 65% RH, using an oxygentransmission tester, Ox-Tran 100 Model (manufactured by Modern ControlInc.).

(2) Contents Preservability:

A tube container sample was filled with “miso” (soy bean paste) throughits bottom opening, which was then heat-sealed. Next, a disc ofaluminium foil (thickness: 25μ) was applied to the mouth, and the tubecontainer was then closed by screwing a cap. The tube container thusfilled with “miso” was allowed to stand in a thermo-hygrostat at 40° C.and 50% RH. After 24 hours, it was taken out, and the “miso” kept incontact with the inner surface of its head was checked with the nakedeye for the degree of discoloration if any. All tube containers preparedherein were evaluated for the “miso” preservability according to thefollowing criteria A to D:

A: Not discolored.

B: Discolored in pale brown.

C: Discolored in brown.

D: Discolored in reddish brown.

(3) Heat-sealability:

The body of a tube container sample was longitudinally cut at 2 pointsin the opposite sides above a line of heat-sealing to the head to obtaina test piece having a width of 15 mm. The cut-out test piece was mountedon a tensile tester with the both edges being fixed, and the peelingstrength of the heat-sealed part was measured at 20° C. and 65% RHaccording to JISK 7127.

A: More than 3.0 kg.

B: From 2.5 to 3.0 kg.

C: From 2.0 to 2.5 kg.

D: Less than 2.0 kg.

(4) Strength of Head:

At 20° C. and 65% RH, a tube container sample was subjected to repeatedcycles of screwing and unscrewing its cap for a total of 30 times. Afterthe cycle test, the sample was checked with the naked eye and with theaid of a magnifier for chips and cracks, if any, in the screw-threadpart of the neck and for cracks, if any, in the head. All tubecontainers prepared herein were tested in that manner and evaluatedaccording to the criteria A to D mentioned below. In screwing the cap,used was a torque meter. Screwing the cap was effected at a torque of 5kg·cm.

A: Neither chips nor cracks found.

B: Minor cracks found through the magnifier.

C: Minor cracks found with the naked eye.

D: Small cracks and chips found with the naked eye.

(5) Outward Appearance of Head:

The head of each tube container sample was checked with the naked eyefor its outward appearance (surface condition, and discoloration andformation of gels and fish eyes, if any). Tube containers producedimmediately after the start of injection molding, and those produced in24 hours after the start thereof were checked in that manner, andevaluated according to the following criteria A to D:

A: Good with no change.

B: Minor gels and fish eyes found, or the surface roughened a little.

C: Definite gels and fish eyes found, or the surface roughened partly.

D: Definite gels and fish eyes found, or the surface roughenedthoroughly. The head discolored in pale yellow.

FIG. 1 shows the outline partly in section of the tube containerproduced in Examples. As illustrated, the cylindrical body 1 isintegrated with the head 2 by heat-sealing at the shoulder 3 of the head2, the head 2 has a male screw 2 a at its top and a shoulder 2 b thatfollows the male screw 2 a, and the body 1 is further integrated withthe heat-sealed bottom 4. FIG. 2 shows the constitution of thecylindrical body 1, which is composed of a heat-seal layer (LDPE) 5, anadhesive resin 6, a barrier resin EVOH 7, an adhesive resin 8 and anouter layer (LDPE) 9 as laminated in that order from inside.

Examples 1-2 to 1-8, and Comparative Examples 1-1 to 1-8

Various tube containers were produced in the same manner as in Example1-1, except that resin pellets shown in Table 5 were used in place ofthe four-component resin pellets in

Example 1-1

Precisely, the resins and their ratios were varied as in Table 5. Toprepare two-component and three-component resin compositions, theconstituent resins were blended in one kneading operation. To prepareone-component resin compositions, the constituent resin was not kneaded.The results of evaluation of those tube containers are shown in Table 5.

Example 1-9

Tube containers were produced in the same manner as in Example 1-1,except that the four resin components were kneaded only once and all ata time, and pelletized. The results of evaluation of the tube containersare shown in Table 5.

TABLE 5 Resin Composition A B C D Component of wt. pts. wt. pts. wt.pts. wt. pts. W(A)/W(A + D) W(B + C)/W(T) W(B)/W(B + C) Matrix PhaseExample 1-1 A-3 B-2 C-1 D-1 0.50 0.20 0.25 D-1 40  5 15 40 Example 1-2A-4 B-2 C-2 D-1 0.50 0.20 0.25 D-1 40  5 15 40 Example 1-3 A-4 B-2 C-1D-1 0.50 0.20 0.25 D-1 40  5 15 40 Example 1-4 A-4 B-2 C-2 D-1 0.47 0.250.40 D-1 35 10 15 40 Example 1-5 A-3 B-1 C-2 D-2 0.63 0.20 0.50 D-2 5010 10 30 Example 1-6 A-4 B-1 C-1 D-2 0.53 0.15 0.47 D-2 45  7  8 40Example 1-7 *2) B-1 C-1 D-2 0.56 0.20 0.50 D-2 45 10 10 35 Example 1-8A-4 B-2 C-2 D-1 0.50 0.20 0.75 D-1 40 15  5 40 Example 1-9 A-4 B-2 C-2D-1 0.50 0.20 0.25 D-1 40  5 15 40 Comparative — — — D-1 0.00 0.00 — D-1Example 1-1 100  Comparative A-4 — — D-1 0.40 0.00 — D-1 Example 1-2 4060 Comparative A-4 B-2 — D-1 0.50 0.20 — D-1 Example 1-3 40 20 40Comparative A-4 — C-1 D-1 0.50 0.20 — D-1 Example 1-4 40 20 40Comparative A-4 — — — 1.00 0.00 — A-4 Example 1-5 100  Comparative A-4B-2 C-2 D-1 0.75 0.20 0.25 A-4 Example 1-6 60  5 15 20 Comparative A-4B-2 C-3 D-1 0.50 0.20 0.25 D-1 Example 1-7 40  5 15 40 Comparative A-4 —C-4 D-1 0.50 0.20 0.25 D-1 Example 1-8 40 20 40 Quality EvaluationAppearance of Head Just after start of 24 hours after OTR *1)Preservability Heat-sealability Strength of Head molding start ofmolding Remarks Example 1-1 16 A A A A A Example 1-2 15 A A A A AExample 1-3 14 A A A A A Example 1-4 40 B A A A A Example 1-5 12 A A B AA Example 1-6 10 A B B A A Example 1-7 13 A A A A A Example 1-8 18 A A AA B Example 1-9 20 A B B B B Kneaded once all at a time. Comparative3300  D A A A A Example 1-1 Comparative 300  C D D C C Example 1-2Comparative 80 B D C D D Example 1-3 Comparative 19 A C C A B Example1-4 Comparative  2 A D C A A Example 1-5 Comparative  7 A C C A AExample 1-6 Comparative 25 A B A A C Example 1-7 Comparative 19 A B C AB Example 1-8 *1) unit: cc · 20 μ/m² · day · atm. *2) A-2 (20 wt. pts.)and A-4 (25 wt. pts.) were used.

EXAMPLES FOR COATABILITY Example 2-1

Of the resins shown in Tables 1 to 4, a blend comprised of 10 parts byweight of EVOH (A-1), 1 part by weight of polyamide (B-1), 2 parts byweight of ionomer (C-2) and 87 parts by weight of polypropylene (D-3)was prepared according to the method mentioned below. Precisely,polyamide (B-1) and ionomer (C-2) were fed into a vent-type, twin-screwextruder, and pelletized through it at 220° C. in the presence ofnitrogen. The resulting blend pellets were further blended with EVOH(A-1) and polypropylene (D-3), in the same manner as above, to obtainthe intended resin composition pellets.

Using an injection-molding machine, FS 80S Model (manufactured by NisseiResin Industry Co.), the resin pellets prepared herein were molded at220° C. into test pieces for mechanical strength and those forcoatability. Observing the test pieces with an electronic microscopeverified that polypropylene (D-3) formed a matrix phase and EVOH (A-1)formed a dispersed phase in the test pieces. The test pieces were testedfor their quality according to the methods mentioned below, and the testresults are shown in Table 6.

(1) Tensile Strength (kg/cm²):

According to ASTM D638, the samples were tested at room temperature.

(2) Breaking Elongation (%):

According to ASTM D638, the samples were tested at room temperature.

(3) Bending Strength (kg/cm²):

According to ASTM D790, the samples were tested at room temperature.

(4) Impact Strength (kg·cm/cm):

According to ASTM D256, each sample having a thickness of 3.2 mm wasnotched and tested at 20° C. and 65% RH.

(5) Coatability:

Each sample was wiped with gauze containing isopropyl alcohol, andcoated with urethane paint without being precoated with primer, and thenbaked at 80° C. for 30 minutes to form a paint layer thereon. Thethus-coated sample was kept at 23° C. and 65% RH for 24 hours or longer,and the adhesion strength (primary adhesion strength) of the paint layerwas measured in a cross-cut peeling test according to JIS D02024. 15.Apart from this, the sample was dipped in hot water at 40° C. for 240hours, and was subjected to the same peeling test to measure theadhesion strength (secondary adhesion strength) of the paint layer. Thesamples tested were evaluated on the basis of their surface condition,and ranked as follows:

A: Good surface gloss with no peeling.

B: No peeling, but the surface gloss lowered a little.

C: No peeling, but the surface gloss lowered greatly.

D: Peeled.

(6) Outward Appearance:

Test pieces were checked with the naked eye for their outward appearance(surface condition, and gels and fish eyes, if any). Those producedimmediately after the start of injection molding and those produced in24 hours after the start thereof were checked in that manner, andevaluated according to the following criteria A to C:

A: Good with no change.

B: Minor gels and fish eyes found, or the surface roughened a little.

C: Definite gels and fish eyes found, and the surface roughened partly.

Examples 2-2 to 2-4, and Comparative Examples 2-1 to 2-6

Various test pieces were produced in the same manner as in Example 2-1,except that resin pellets shown in Table 6 were used in place of thefour-component resin pellets in Example 2-1. Precisely, the resins andtheir ratios were varied as in Table 6. To prepare two-component andthree-component resin compositions, the constituent resins were blendedin one kneading operation. To prepare one-component resin compositions,the constituent resin was not kneaded. The results of evaluation ofthose test pieces are shown in Table 6.

Example 2-5

Test pieces were produced in the same manner as in Example 2-1, exceptthat the four resin components were kneaded only once and all at a time,and pelletized. The results of evaluation of the test pieces are shownin Table 6.

TABLE 6 Resin Composition A B C D Component of wt. pts. wt. pts. wt.pts. wt. pts. W(A)/W(A + D) W(B + C)/W(T) W(B)/W(B + C) Matrix PhaseExample 2-1 A-1 B-1 C-2 D-3 0.10 0.03 0.33 D-3 10 1 2 87 Example 2-2 A-2B-2 C-1 D-3 0.16 0.05 0.40 D-3 15 2 3 80 Example 2-3 A-5 B-1 C-2 D-30.07 0.03 0.67 D-3  7 2 1 90 Example 2-4 *1) B-2 C-1 D-3 0.16 0.05 0.80D-3 15 4 1 80 Example 2-5 A-1 B-1 C-2 D-3 0.10 0.03 0.33 D-3 10 1 2 87Comparative A-1 — — D-3 0.10 0.00 — D-3 Example 2-1 10 90 ComparativeA-1 B-1 — D-3 0.10 0.03 — D-3 Example 2-2 10 3 87 Comparative A-1 — C-2D-3 0.10 0.03 — D-3 Example 2-3 10 3 87 Comparative — — — D-3 — 0.00 —D-3 Example 2-4 100  Comparative A-1 B-1 C-2 D-3 0.79 0.03 0.33 A-1Example 2-5 77 1 2 20 Comparative A-1 B-1 C-3 D-3 0.10 0.03 0.33 D-3Example 2-6 10 1 2 87 Quality Evaluation Appearance Tensile BreakingBending Impact Coat Film Adhesiveness Just after X hours after StrengthElongation Strength Strength Primary Secondary start of start of(kg/cm²) (kg/cm²) (kg/cm²) (kg/cm²) Adhesion Adhesion molding moldingRemarks Example 2-1 360 90 520 4.5 A A A A Example 2-2 370 80 550 4.6 AA A A Example 2-3 360 95 530 4.5 A A A B Example 2-4 380 92 540 4.8 A AA B Example 2-5 340 80 500 4.2 A B B B Kneaded once all at a time.Comparative 350 10 580 2.2 A D C C Example 2-1 Comparative 360 30 5502.5 A C B C Example 2-2 Comparative 350 50 540 2.9 A C A B Example 2-3Comparative 370 110  550 4.6 D D A A Example 2-4 Comparative 550 20 6001.5 A A B B Example 2-5 Comparative 360 80 500 3.5 A B A C Example 2-6*1) A-3 (5 wt. pts.) and A-5 (10 wt. pts.) were used.

EXAMPLES FOR SCRAP RECYCLABILITY Example 3-1

The resins used in the following Examples are those in Tables 1 to 4.

First prepared was a three-layered sheet (560 μm/100 μm/560 μm) havingouter polypropylene (PP; D-4) layers on the both surfaces of an EVOH(A-2) layer, through co-extrusion. This was ground into scrap[(A-2)/(D-4)=10/86, parts by weight].

On the other hand, 1 part by weight of polyamide (B-1) and 3 parts byweight of ionomer (C-3) were fed into a vent-type, twin-screw extruder,and pelletized through it at 220° C. in the presence of nitrogen.

Next, 96 parts by weight of the scrap comprised of EVOH (A-2) andpolypropylene (D-4) were mixed with 4 parts by weight of the resinpellets comprised of polyamide (B-1) and ionomer (C-2), and pelletizedthrough a fullflight-type, single-screw extruder.

As a result of the process noted above, obtained were resin compositionpellets (hereinafter referred to as REG) comprised of 10 parts by weightof EVOH (A-2), 1 part by weight of polyamide (B-1), 3 parts by weight ofionomer (C-3) and 86 parts by weight of polypropylene (D-4).

The thus-obtained, four-component resin composition pellets, EVOH (A-2),polypropylene (D-4) and adhesive resin (maleic anhydride-modifiedpolypropylene) were put into separate extruders, and co-extruded, usinga 4-type/7-layer co-extrusion apparatus, into a 7-layered sheet (overallthickness: 1000μ) having a constitution of PP/REG/adhesiveresin/EVOH/adhesive resin/REG/PP (300/150/25/50/25/150/300 μ).Precisely, PP was extruded through a single-screw (65 mmφ) extruder at240° C.; REG through a single-screw (40 mmφ) extruder at 220° C.; theadhesive resin through a single-screw (40 mmφ) extruder at 220° C.; andEVOH through a single-screw (40 mmφ) extruder at 210° C. 24 hours andeven 72 hours after the start of extrusion, the sheets obtained were allhad good outward appearance, without showing wavy patterns anddelamination that might be caused by poor compatibility and bad flow, ifany, of REG. Observing the REG layers of the sheets obtained herein withan electronic microscope verified that polypropylene (D-4) formed amatrix phase and EVOH (A-2) formed a dispersed phase in the layers.

Using a thermoforming machine (manufactured by Asano Seisaku-sho Co.),the sheets obtained in 24 hours and 72 hours after the start ofextrusion were thermoformed into cups (size of mold: 70φ×70 mm). Thethermoforming condition was as follows: The pressure of compression airintroduced was 5 kg/cm2; the plug was of syntactic foam and its size was45φ×65 mm; the sheet temperature was 150° C.; the plug temperature was20° C., and the mold temperature was 70° C. Each cup formed was checkedwith the naked eye for its outward appearance. Like the sheets notedabove, the cups formed therefrom all had good outward appearance,without showing wavy patterns and delamination that might be caused bypoor compatibility and bad flow, if any, of blend pellets of REG.

The sheets and the cups were evaluated for their outward appearanceaccording to the following criteria:

A: Good and uniform surface with neither wavy patterns nor delamination.

B: Good and uniform surface with no delamination, but minor wavypatterns found partly.

C: Definite wavy patterns and delamination found on the whole surface.

D: Definite wavy patterns, delamination, gels and fish eyes found on thewhole surface.

The results obtained are shown in Table 7.

Examples 3-2 to 3-5, and Comparative Examples 3-1 to 3-6

Various resin compositions were produced in the same manner as inExample 3-1, except that resin pellets shown in Table 7 were used inplace of the four-component resin pellets in Example 3-1. Precisely, theresins and their ratios were varied as in Table 7 to prepare resinpellets herein. To prepare two-component and three-component resincompositions, the constituent resins were blended in one kneadingoperation.

Seven-layered sheets having the same constitution as in Example 3-1 wereproduced in the same manner as in Example 3-1, except that the resincompositions prepared herein were used. These sheets were thermoformedinto cups and the cups were evaluated, also in the same manner as inExample 3-1. The results obtained are shown in Table 7.

Example 3-6

A resin composition was produced in the same manner as in Example 3-1,except that 1 part by weight of calcium stearate (manufactured by NipponOils & Fats Co.) was added to 4 parts by weight of the blend ofpolyamide (B-1) and ionomer (C-2) (blending ratio: 25/75 by weight) usedin Example 3-1.

Seven-layered sheets having the same constitution as in Example 3-1 wereproduced in the same manner as in Example 3-1, except that the resincomposition prepared herein was used. The sheets were thermoformed intocups and the cups were evaluated, also in the same manner as in Example3-1. The results obtained are shown in Table 7.

Example 3-7

A resin composition was produced in the same manner as in Example 3-1and Example 3-6, except that hydrotalcite (DHT-4A, manufactured by KyowaChemical Co.) was used in place of calcium stearate used in Example 3-6.

Seven-layered sheets having the same constitution as in Example 3-1 wereproduced in the same manner as in Example 3-1, except that the resincomposition prepared herein was used. The sheets were thermoformed intocups and the cups were evaluated, also in the same manner as in Example3-1. The results obtained are shown in Table 7.

Example 3-8

A resin composition was produced in the same manner as in Example 3-1,except that all the four components were pelletized through one kneadingoperation where they were kneaded once all at a time withoutpre-kneading polyamide (B-1) and ionomer (C-2).

Seven-layered sheets having the same constitution as in Example 3-1 wereproduced in the same manner as in Example 3-1, except that the resincomposition prepared herein was used. The sheets were thermoformed intocups and the cups were evaluated, also in the same manner as in Example3-1. The results obtained are shown in Table 7.

Example 3-9

A four-component resin composition (REG) was prepared in the same manneras in Example 3-1, except for the following points: Precisely,polystyrene (PS; D-5) was used herein in place of polypropylene (D-4),and a three-layered sheet having outer polystyrene (D-5) layers on theboth surfaces of an EVOH (A-2) layer (490/100/490 μ) was formed throughco-extrusion. The sheet: was ground into scrap, and the scrap thusprepared was used herein.

The four-component resin composition pellets obtained herein, EVOH(A-2), polystyrene (D-5) and adhesive resin (maleic anhydride-modifiedethylene-vinyl acetate copolymer) were put into separate extruders, andco-extruded, using a 4-type/7-layer co-extrusion apparatus, into a7-layered sheet (overall thickness: 1000 μ) having a constitution ofPS/REG/adhesive resin/EVOH/adhesive resin/REG/PS(300/150/25/50/25/150/300 μ). Precisely, PS was extruded through asingle-screw (65 mmφ) extruder at 240° C.; REG through a single-screw(40 mmφ) extruder at 220° C.; the adhesive resin through a single-screw(40 mmφ) extruder at 220° C.; and EVOH through a single-screw (40 mmφ)extruder at 210° C.

Using a thermoforming machine (manufactured by Asano Seisaku-sho Co.),the sheets obtained in 24 hours and 72 hours after the start ofextrusion were thermoformed into cups (size of mold: 70φ×70 mm). Thethermoforming condition was as follows: The pressure of compression airintroduced was 5 kg/cm2; the plug was of syntactic foam and its size was45φ×65 mm; the sheet temperature was 130° C.; the plug temperature was20° C., and the mold temperature was 70° C.

The cups were evaluated, and the results are shown in Table 8.

Examples 3-10 to 3-12, and Comparative Examples 3-6 to 3-9

Various resin compositions were produced in the same manner as inExample 3-9, except that resin pellets shown in Table 8 were used inplace of the four-component resin pellets in Example 3-9. Precisely, theresins and their ratios were varied as in Table 8 to prepare resinpellets herein. To prepare two-component and three-component resincompositions, the constituent resins were blended in one kneadingoperation.

Seven-layered sheets having the same constitution as in Example 3-9 wereproduced in the same manner as in Example 3-9, except that the resincompositions prepared herein were used. These sheets were thermoformedinto cups and the cups were evaluated, also in the same manner as inExample 3-9. The results obtained are shown in Table 8.

Comparative Example 3-10

A four-component resin composition (REG) was prepared in the same manneras in Example 3-1, except for the following points: Precisely,polyethylene terephthalate (PET; D-7) was used herein in place ofpolypropylene (D-4), and a three-layered sheet having outer polyethyleneterephthalate (D-7) layers on the both surfaces of an EVOH (A-2) layer(370/100/370 μ) was formed through co-extrusion. The sheet was groundinto scrap, and the scrap thus prepared was used herein.

The four-component resin composition pellets obtained herein, EVOH(A-2), polyethylene terephthalate (D-7) and adhesive resin (maleicanhydride-modified ethylene-vinyl acetate copolymer) were put intoseparate extruders, and co-extruded, using a 4-type/7-layer co-extrusionapparatus, into a 7-layered sheet (overall thickness: 1000 μ) having aconstitution of PET/REG/adhesive resin/EVOH/adhesive resin/REG/PET(300/150/25/50/25/150/300 μ). Precisely, PET was extruded through asingle-screw (65 mmφ) extruder at 270° C.; REG through a single-screw(40 mmφ) extruder at 220° C.; the adhesive resin through a single-screw(40 mmφ) extruder at 270° C.; and EVOH through a single-screw (40 mmφ)extruder at 210° C.

Using a thermoforming machine (manufactured by Asano Seisaku-sho Co.),the sheets obtained in 24 hours and 72 hours after the start ofextrusion were thermoformed into cups (size of mold: 70φ×70 mm). Thethermoforming condition was as follows: The pressure of compression airintroduced was 5 kg/cm2; the plug was of syntactic foam and its size was45φ×65 mm; the sheet temperature was 110° C.; the plug temperature was20° C., and the mold temperature was 70° C.

The cups were evaluated, and the results are shown in Table 8.

Comparative Example 3-11

A resin composition was produced in the same manner as in Example 3-10,except that resin pellets shown in Table 8 were used in place of thefour-component resin pellets in Example 3-10. Precisely, the resins andtheir ratios were varied as in Table 8 to prepare resin pellets herein.To prepare the resin composition, the constituent resins were blended inone kneading operation.

Seven-layered sheets having the same constitution as in Example 3-10were produced in the same manner as in Example 3-10, except that theresin composition prepared herein was used. These sheets werethermoformed into cups and the cups were evaluated, also in the samemanner as in Example 3-10. The results obtained are shown in Table 8.

TABLE 7 Resin Composition A B C D Additive W(B) Matrix wt. pts. wt. pts.wt. pts. wt. pts. wt. pts. W(A)/W(A + D) W/(B + C)/W(T) /W(B + C)Component Example 3-1 A-2 B-1 C-2 D-4 — 0.10 0.04 0.25 D-4 10 1 3 86Example 3-2 A-2 B-1 C-2 D-4 — 0.10 0.04 0.75 D-4 10 3 1 86 Example 3-3A-2 B-1 C-2 D-4 — 0.16 0.05 0.40 D-4 15 2 3 80 Example 3-4 A-3 B-1 C-2D-4 — 0.21 0.06 0.50 D-4 20 3 3 74 Example 3-5 A-3 B-2 C-1 D-4 — 0.100.04 0.25 D-4 10 1 3 86 Example 3-6 A-3 B-2 C-1 D-4 St-Ca 0.10 0.04 0.25D-4 10 1 3 86 1 Example 3-7 A-3 B-2 C-1 D-4 DHT-4A 0.10 0.04 0.25 D-4 101 3 86 Example 3-8 A-2 B-1 C-2 D-4 — 0.10 0.04 0.25 D-4 10 1 3 86Comparative A-2 — — D-4 — 0.10 0.00 — D-4 Example 3-1 10 90 ComparativeA-2 — C-2 D-4 — 0.10 0.03 — D-4 Example 3-2 10 3 87 Comparative A-2 B-1— D-4 — 0.10 0.01 — D-4 Example 3-3 10 1 89 Comparative A-2 B-1 — D-4 —0.10 0.04 — D-4 Example 3-4 10 4 86 Comparative A-2 B-1 C-3 D-4 — 0.100.04 0.05 D-4 Example 3-5 10 1 3 86 Comparative A-2 — C-4 D-4 — 0.160.05 — D-4 Example 3-6 15 5 80 Appearance of Shaped Articles 24 hoursafter start of sheet molding 72 hours after start of sheet moldingSheets Cups Sheets Cups Remarks Example 3-1 A A A A Example 3-2 A B B CExample 3-3 A B A B Example 3-4 B B B B Example 3-5 A A B B Example 3-6A A A A Example 3-7 A A A A Example 3-8 B B B C Kneaded once all at atime. Comparative D D D D Example 3-1 Comparative D D D D Example 3-2Comparative D D D D Example 3-3 Comparative D D D D Example 3-4Comparative B C C D Example 3-5 Comparative B C B C Example 3-6

TABLE 8 Resin Composition A B C D Additive W(B) Matrix wt. pts. wt. pts.wt. pts. wt. pts. wt. pts. W(A)/W(A + D) W/(B + C)/W(T) /W(B + C)Component Example 3-9 A-2 B-1 C-2 D-5 — 0.10 0.04 0.25 D-5 10 1 3 86Example 3- A-2 B-1 C-2 D-5 — 0.10 0.04 0.75 D-5 10 10 3 1 86 Example 3-A-2 B-2 C-1 D-5 — 0.16 0.05 0.40 D-5 11 15 2 3 80 Example 3- A-3 B-2 C-1D-5 — 0.08 0.04 0.33 D-5 12 8 1 2 89 Comparative A-2 — — D-5 — 0.10 0.03— D-5 Example 3-6 10 90 Comparative A-2 — C-2 D-5 — 0.10 0.00 — D-5Example 3-6 10 4 86 Comparative A-2 B-1 — D-5 — 0.10 0.04 — D-5 Example3-8 10 4 86 Comparative A-2 B-1 C-3 D-5 — 0.10 0.04 0.25 D-5 Example 3-910 1 3 86 Comparative A-2 B-1 C-2 D-7 — 0.10 0.04 0.25 D-7 Example 3- 101 3 86 10 Comparative A-2 — — D-7 — 0.10 0.00 — D-7 Example 3- 10 90 11Appearance of Shaped Articles 24 hours after start of sheet molding 72hours after start of sheet molding Sheets Cups Sheets Cups Example 3-9 AA A A Example 3-10 A B B B Example 3-11 A B A B Example 3-12 A A A BComparative D D D D Example 3-6 Comparative D D D D Example 3-7Comparative D D D D Example 3-8 Comparative C D D D Example 3-9Comparative D D D D Example 3-10 Comparative D D D D Example 3-11

EXAMPLES OF FLEXIBLE FILM Example 4-1

Of the resins shown in Tables 1 to 4, a blend comprised of 90 parts byweight of EVOH (A-2), 1 part by weight of polyamide (B-1), 1 part byweight of ionomer (C-2) and 8 parts by weight of very-low-densitypolyethylene (D-6) was prepared according to the method mentioned below.Precisely, polyamide (B-1) and ionomer (C-2) were fed into a vent-type,twin-screw extruder, and pelletized through it at 220° C. in thepresence of nitrogen. The resulting blend pellets were further blendedwith EVOH (A-2) and very-low-density polyethylene (D-6), in the samemanner as above, to obtain the intended resin composition pellets.

Using a fullflight-type screw extruder (40 mmφ, L/D=24, compressionratio=3.5), the thus-obtained pellets were extruded through a flat diehaving a width of 550 mm into a single-layered film having a thicknessof 25 μ. Observing the film thus obtained herein with an electronicmicroscope verified that EVOH (A-2) formed a matrix phase and thevery-low-density polyethylene (D-6) formed a dispersed phase in thefilm. According to the methods mentioned below, the film was tested forthe haze, the bending resistance, the Young's modulus, the film impact,the oxygen transmission rate (OTR), and, if any, gels and fish eyes. Theresults obtained are shown in Table 9.

(1) Haze:

The haze of a film sample having a thickness of 25 μ was measured, usinga Poic integrating-sphere light transmittance meter (manufactured byNippon Seimitsu Kogaku KK).

(2) Bending Resistance:

The bending resistance of each film sample was measured, using a GelboFlex Tester (manufactured by Rigaku Kogyo KK). Precisely, a film samplehaving a size of 12 inches×8 inches was rounded into a cylindrical filmhaving a diameter of 3.5 inches, and the both edges of the cylindricalfilm were fixed. The original distance between the both edges fixed was7 inches. With its one edge being moved, the cylindrical film wassubjected to reciprocating motion of 40 strokes/min in the followingmanner: In one stroke, the sample was twisted at 440 degrees in thefirst 3.5 inches, while it was linearly moved in the horizontaldirection in the next 2.5 inches. The distance between the both edges atthe greatest stroke was 1 inch. 100 strokes were repeated for one sampleat 20° C. and 65% RH, and the number of pinholes, if any, formed in thesample after the test was counted.

In the same bending test, the number of strokes to give the firstpinhole in the sample was counted.

(3) Young's Modulus:

The Young's modulus of each film sample was measured at 20° C. and 65%RH, according to ASTM D-882-67.

(4) Film Impact:

A disc film sample having a predetermined area was holded horizontally,and a stick having 0.6-inch semi-ball at its tip was vertically appliedthereto, and the force to the stick at which the film was broken wasread out. Prior to this test, the film sample was pre-conditioned at 20°C. and 65% RH for 2 weeks. The device used in this test was Film ImpactTester manufactured by Toyo Seiki KK.

(5) Oxygen Transmission Rate (OTR):

The oxygen transmission rate (OTR) through each film sample was measuredat 20° C. and 65% RH, using OX-Tran10-50A (manufactured by ModernControl Co.).

(6) Gels and Fish Eyes:

Film samples produced in 24 hours after the start of film-formingextrusion were checked with the naked eye, and evaluated according tothe following criteria A to D:

A: Neither gels nor fish eyes found.

B: Minor gels and fish eyes formed.

C: Small gels and fish eyes formed partly on the surface.

D: Small gels and fish eyes formed thoroughly on the surface.

Examples 4-2 to 4-6, and Comparative Examples 4-1 to 4-9

Various single-layered films were produced in the same manner as inExample 4-1, except that resin pellets shown in Table 9 were used inplace of the four-component resin pellets in Example 4-1. Precisely, theresins and their ratios were varied as in Table 9. To preparetwo-component and three-component resin compositions, the constituentresins were blended in one kneading operation. To prepare one-componentresin compositions, the constituent resin was not kneaded. The resultsof evaluation of those films are shown in Table 9.

Example 4-7

Single-layered films were produced in the same manner as in Example 4-1,except that the four resin components were kneaded only once and all ata time, and pelletized. The results of evaluation of the films are shownin Table 9.

TABLE 9 Resin Composition A B C D Component of wt. pts. wt. pts. wt.pts. wt. pts. W(A)/W(A + D) W(B + C)/W(T) W(B)/W(B + C) Matrix PhaseExample 4-1 A-2 B-1 C-2 D-6 0.92 0.02 0.50 A-2 90 1 1  8 Example 4-2 A-2B-1 C-2 D-6 0.84 0.05 0.40 A-2 80 2 3 15 Example 4-3 A-2 B-1 C-2 D-60.74 0.05 0.40 A-2 70 2 3 25 Example 4-4 A-2 B-1 C-2 D-6 0.84 0.05 0.80A-2 80 4 1 15 Example 4-5 A-2 B-1 C-2 D-8 0.84 0.05 0.40 A-2 80 2 3 15Example 4-6 A-2 B-1 C-1 D-6 0.84 0.05 0.40 A-2 80 2 3 15 Example 4-7 A-2B-1 C-2 D-6 0.84 0.05 0.40 A-2 80 2 3 15 Comparative A-1 — — D-6 0.800.00 — A-1 Example 4-1 80 20 Comparative A-2 B-1 — D-6 0.84 0.05 — A-2Example 4-2 80 5 15 Comparative A-2 — C-2 D-6 0.84 0.05 — A-2 Example4-3 80 5 15 Comparative A-2 B-1 C-2 — 1.00 0.20 0.25 A-2 Example 4-4 807 13  Comparative A-1 — — — 1.00 0.00 — A-1 Example 4-5 100  ComparativeA-2 B-1 C-3 D-6 0.84 0.05 0.40 A-2 Example 4-6 80 2 3 15 Comparative A-2B-1 C-2 D-1 0.84 0.05 0.40 A-2 Example 4-7 80 2 3 15 Comparative A-2 B-1C-2 D-9 0.84 0.05 0.40 A-2 Example 4-8 80 2 3 15 Comparative A-1 — — D-90.80 0.00 — A-1 Example 4-9 80 20 Quality Evaluation Bending Resistance(number of (number of strokes before Young's pinholes formation ofModulus Film Impact OTR Haze (%) formed) pinholes) (kg/cm²) (kg · cm)*1) Gel Fish Eyes Remarks Example 4-1 10 0 100 165 2.5 2.6 A Example 4-212 0 180 140 3.2 2.9 A Example 4-3 15 0 250 110 3.8 3.3 A Example 4-4 13— 170 140 2.6 2.8 B Example 4-5 12 — 210 100 3.3 3.0 A Example 4-6 13 —190 120 2.8 3.1 A Example 4-7 11 — 180 125 2.5 3.1 A Kneaded once all ata time. Comparative 20 0 200 120 0.5 3.1 B Example 4-1 Comparative 19 —150 145 0.8 2.8 C Example 4-2 Comparative 19 — 200 120 0.6 3.2 B Example4-3 Comparative  5 — 120 160 1.9 2.8 C Example 4-4 Comparative  1 40  40 200 0.9 2.1 A Example 4-5 Comparative 15 — 150 150 1.9 3.1 C Example4-6 Comparative 15 —  80 170 1.2 3.3 A Example 4-7 Comparative 12 — 200100 0.7 3.2 D Example 4-8 Comparative 12 — 250  90 0.5 3.5 D Example 4-9

EXAMPLES OF MAT FILM Example 5-1

85% by weight of EVOH pellets having an ethylene content of 44 mol %, adegree of saponification of 99.4 mol % and a melt index of 5.1 g/10 min(measured at 190° C. and under a load of 2160 g), 10% by weight ofhigh-density polyethylene resin having a melt index of 1.0 g/10 min(measured at 190° C. and under a load of 2160 g), 2% by weight ofpolyamide resin (PA-6, Toray's Amilan CN1010T), and 3% by weight ofethylene-methacrylic acid copolymer (having a methacrylic acid contentof 3.1 mol %, and a melt index of 1.5 g/10 min as measured at 190° C.and under a load of 2160 g) were blended and pelletized, using atwin-screw extruder. The resulting pellets were formed into a filmhaving a thickness of 20 μm, through a single-screw extruder equippedwith a T-die. This film had a degree of surface gloss of 35%. Observingthe film with an electronic microscope verified that EVOH formed amatrix phase and the high-density polyethylene formed a dispersed phase.

The outward appearance of the film having been produced in 8 hours afterthe start of film-forming extrusion was checked with the naked eye forgels and fish eyes, if any, and the film was evaluated according to thefollowing criteria A to D:

A: Neither gels nor fish eyes found.

B: Minor gels and fish eyes formed.

C: Small gels and fish eyes formed partly on the surface.

D: Small gels and fish eyes formed thoroughly on the surface.

Examples 5-2 to 5-9, and Comparative Examples 5-1 to 5-7

Various films were produced in the same manner as in Example 5-1, exceptthat the constituent resins and their amounts were varied. The degree ofsurface gloss of those films was measured, and the outward appearancethereof was checked. The resins and their amounts used herein are shownin Table 10 along with the test data obtained.

The following were used herein as the EVOH (A).

a-1

EVOH, having an ethylene content of 44 mol %, a degree of saponificationof 99.4%, and a melt index of 5.1 g/10 min (190°C, 2160 g).

a-2

EVOH, having an ethylene content of 27 mol %, a degree of saponificationof 99.4%, and a melt index of 1.5 g/10 min (190° C., 2160 g).

The following were used as the polyamide (B):

b-1

6-Polyamide (Toray's Amilan CN1010T).

b-2

6/12-Copolyamide (UBE Nylon 7024B).

The following were used as the ethylene-unsaturated carboxylic acidrandom copolymer or its metal salt (C).

c-1

Ethylene-methacrylic acid random copolymer, having a methacrylic acidcontent of 3.1 mol %, and a melt index of 1.5 g/10 min (190° C., 2160g).

c-2

Metal salt (ionomer) of ethylene-methacrylic acid random copolymer,having a methacrylic acid content of 5.3 mol %, a degree ofneutralization of 60% with a counter ion of Zn, and a melt index of 0.7g/10 min (190° C., 2160 g).

c-3

Metal salt (ionomer) of ethylene-methacrylic acid random copolymer,having a methacrylic acid content of 6.7 mol %, a degree ofneutralization of 36% with a counter ion of Na, and a melt index of 2.1g/10 min (190° C., 2160 g).

The following were used as the thermoplastic resin (D).

d-1

High-density polyethylene, having a melt index of 1.0 g/10 min (190° C.,2160 g).

d-2

Low-density polyethylene, having a melt index of 2.5 g/10 min (190° C.,2160g ).

d-3

Maleic anhydride-modified high-density polyethylene, having a degree ofmodification of 0.09 mol %, and a melt index of 1.0 g/10 min (190° C.,2160 g).

TABLE 10 Resin Composition A B C D Additive W(A) W(B + C) W(B) MatrixSurface Gel Fish wt. pts. wt. pts. wt. pts. wt. pts. wt. pts. /W(A + D)/W(T) /W(B + C) Component Gloss (%) Eyes Example 5- a-1 b-1 c-1 d-1 —0.89 0.05 0.29 a-1 36 A 1 85 2 3 10 Example 5- a-1 b-1 c-2 d-1 — 0.760.15 0.47 a-1 11 B 2 65 7 8 20 Example 5- a-1 b-1 c-2 d-1 — 0.83 0.100.40 a-1 19 A 3 75 4 6 15 Example 5- a-1 b-2 c-2 d-1 — 0.83 0.10 0.40a-1 24 A 4 75 4 6 15 Example 5- a-1 b-1 c-2 d-2 — 0.83 0.10 0.40 a-1 16A 5 75 4 6 15 Example 5- a-2 b-1 c-2 d-1 — 0.83 0.10 0.40 a-2 20 A 6 754 6 15 Example 5- a-2 b-1 c-3 d-2 — 0.83 0.10 0.40 a-2 27 A 7 75 4 6 15Example 5- a-2 b-2 c-1 d-2 — 0.83 0.10 0.40 a-2 30 A 6 75 4 6 15 Example5- a-1 b-1 c-1 d-3 — 0.83 0.1 0.40 a-1 16 A 9 75 4 6 15 Comp. Ex. a-1 —— d-1 — 0.75 0 — a-1 70 A 5-1 75 25 Comp. Ex. a-1 b-1 — d-1 — 0.83 0.1 —a-1 78 C 5-2 75 10  15 Comp. Ex. a-1 — c-2 d-1 — 0.83 0.1 — a-1 75 A 5-375 10  15 Comp. Ex. a-1 b-1 c-2 — — 1.00 0.25 0.78 a-1 90 D 5-4 75 1213  Comp. Ex. a-1 — — d-3 — 1.00 0.00 — a-1 25 D 5-5 75 25 Comp. Ex. a-1b-1 c-2 d-1 — 0.75 0.10 0.80 a-1 25 D 5-6 75 8 2 15 Comp. Ex. a-1 — — —silica 1.00 0.00 — a-1 *i) — 5-7 80 20 *1) Films could not be formed asbeing in holes.

Example 5-10

To prepare a model of polyvinyl chloride wallpaper, 100 parts by weightof polyvinyl chloride (P=1400), 45 parts by weight of dioctyl phthalate,5 parts by weight of tricresyl phosphate, 1 part by weight of epoxyresin stabilizer (trade name: EP-828), 1 part by weight of liquid,barium-zinc composite stabilizer, 0.2 parts by weight of bariumstearate, 0.4 parts by weight of zinc stearate, and 1.5 parts by weightof sorbitan monostearate, were stirred and mixed in a super mixer for 10minutes, then kneaded with mixing rolls heated at 165° C., and sheetedinto a polyvinyl chloride film having a thickness of 0.1 mm. This filmwas laminated with a film of the EVOH composition that had been producedin Example 5-1, using an urethane adhesive AD-335A and a curing agentCat-10 (manufactured by Toyo Moton Co.; mixing ratio=17/1). Theresulting laminate was tested for the stain resistance, the bleedingresistance and the surface gloss. The results obtained are shown inTable 11.

The stain resistance of the EVOH film laminated was evaluated asfollows: Using writing materials of an aqueous ink marker (Sakura's SignPen), an oily ink marker (Zebra's Mackie Gokuboso for drawing ultra-thinlines), a lipstick (Shiseido's Lechente Rouge Excellent RD524), and acrayon (Sakura's Crayon Futomaki Red for drawing thick lines), lineswere drawn on the EVOH film surface of each laminate sample. Thethus-stained samples were wiped with neutral detergent (Lion'sMamalemon). In addition, the samples stained with the oily ink markerwere wiped with a thinner for household use. The thus-wiped samples werechecked for the degree of coloration in the stained area, while beingcompared with a JIS gray scale. The bleeding resistance of the laminatesamples was evaluated as follows: Two laminate samples were put togetherwith their EVOH film surfaces facing each other, and kept at 70° C.under a load of 100 g/cm for 24 hours. After having been thus left, theEVOH film surfaces were checked with the naked eye for their condition.

Comparative Example 5-8

The polyvinyl chloride film of Example 5-10 not laminated with the EVOHfilm was tested and evaluated in the same manner as in Example 5-10. Theresults are shown in Table 11.

TABLE 11 Staining Cleaning Comparative Substance Reagent Example 5-10Example 5-8 Stain Aqueous Ink Neutral 5 4 Resistance Detergent CrayonNeutral 5 4 Detergent Lipstick Neutral 4 to 5 3 Detergent Oily InkNeutral 4 1 Detergent Oily Ink Thinner 5 Substrate dissolved. BleedingNo change in Sealed, and Resistance appearance. peeling impossible.Degree of Sur- 36 73 face Gloss (%)

Comparing Example 5-10 and Comparative Example 5-8, it is obvious thatthe surface gloss of the laminate film of the former is much lower thanthat of the non-laminated film of the latter. In addition, it is knownthat the stain resistance and the bleeding resistance of the laminatefilm of Example 5-10 are much better than those of the non-laminate filmof Comparative Example 5-8.

Industrial Applicability

The invention provides a resin composition comprising (A) anethylene-vinyl alcohol copolymer, (B) a polyamide resin, (C) anethylene-unsaturated carboxylic acid random copolymer or its metal salt,and (D) a thermoplastic resin except the resins noted above, of whichthe solubility parameter (as calculated from the Fedors' formula) is notmore than 11, and having excellent compatibility. The resin compositionhas excellent barrier properties, mechanical strength, flexibility,drawability, melt stability, scrap recyclability, heat sealability,coatability, stain resistance and transparency, and has manyapplications in various fields.

What is claimed is:
 1. A resin composition comprising (A) anethylene-vinyl alcohol copolymer, (B) a polyamide resin, (C) anethylene-unsaturated carboxylic acid random copolymer or its metal salt,and (D) a thermoplastic resin except the resins noted above, of whichthe solubility parameter (as calculated from the Fedors' formula) is notmore than 11, wherein; the compositional ratio by weight satisfies thefollowing formulae (1) to (4): 0.6≦W(A+D)/W(T)≦0.995  (1)0.005≦W(B+C)/W(T)≦0.4  (2) 0.01≦W(A)/W(A+D)≦0.99  (3)0.02≦W(B)/W(B+C)≦0.98  (4)  wherein; W(A) indicates the weight of (A) inthe composition, W(B) indicates the weight of (B) in the composition,W(C) indicates the weight of (C) in the composition, W(D) indicates theweight of (D) in the composition, W(T) indicates the total weight of thecomposition.
 2. The resin composition as claimed in claim 1, whichcontains from 0.01 to 3 parts by weight, based on the total weight ofthe composition, of at least one selected from the group consisting ofmetal salts of higher aliphatic carboxylic acids and hydrotalcitecompounds.
 3. The resin composition as claimed in claim 1, wherein thecompositional ratio by weight of W(B)/W(B+C) is not more than 0.5. 4.The resin composition as claimed in claim 1, wherein the thermoplasticresin (D) forms a matrix phase and the ethylene-vinyl alcohol copolymer(A) forms a dispersed phase.
 5. The resin composition as claimed inclaim 1, wherein the ethylene-vinyl alcohol copolymer (A) forms a matrixphase and the thermoplastic resin (D) forms a dispersed phase.
 6. Theresin composition as claimed in claim 5, wherein the thermoplastic resin(D) has a modulus of elasticity at 20° C. of not more than 500 kg/cm².7. A method for producing the resin composition of claim 1, whichcomprises mixing a polyamide resin (B) and an ethylene-unsaturatedcarboxylic acid random copolymer or its metal salt (C) both in meltfollowed by mixing the resulting melt mixture with an ethylene-vinylalcohol copolymer (A) and a thermoplastic resin (D) all in melt.
 8. Amultilayered structure comprising at least one layer of the resincomposition of claim
 1. 9. A head of a tube container comprising theresin composition of claim
 4. 10. A shaped article comprising the resincomposition of claim 4, of which the surface is painted.
 11. Athermoformed container having a layer of the resin composition of claim4.
 12. A flexible film comprising the resin composition of claim
 5. 13.A mat film comprising the resin composition of claim 5, of which atleast one surface has a degree of surface gloss of not more than 60%.14. A scrap recycling method of using (B) a polyamide resin and (C) anethylene-unsaturated carboxylic acid random copolymer or its metal saltas the compatibilizer for recycling the scrap of shaped articles thatcomprise, as the major components, (A) an ethylene-vinyl alcoholcopolymer and (D) a thermoplastic resin except the resins noted above,of which the solubility parameter (as calculated from the Fedors'formula) is not more than
 11. 15. The scrap recycling method as claimedin claim 14, wherein the compatibilizer contains at least one selectedfrom the group consisting of metal salts of higher aliphatic carboxylicacids and hydrotalcite compounds.
 16. A multilayered structurecomprising at least one scrap-recycled layer of the resin composition asrecycled according to the method of claim
 14. 17. The resin compositionas claimed in claim 1, wherein said ethylene-vinyl alcohol copolymer (A)has an ethylene content of from 15-70 mol %.
 18. The resin compositionas claimed in claim 5, wherein the thermoplastic resin (D) has a modulusof elasticity at 20° C. of not more than 400 kg/cm².
 19. The resincomposition according to claim 1, wherein said ethylene-vinyl alcoholcopolymer (A) has a melt index at 190° C. under a load of 2160 g of from0.1-50 g/10 min.; said polyamide resin (B) has a melt index at 210° C.under a load of 2160 g of from 0.1-50 g/10 min.; saidethylene-unsaturated carboxylic acid random copolymer (C) or its metalsalt has a melt index at 190° C. under a load of 2160 g of from 0.05-50g/10 min.; and said thermoplastic resin (D) has a melt index at 190° C.under a load of 2160 g of from 0.05-100 g/10 min.
 20. The resincomposition according to claim 1, wherein the compositional ratio byweight satisfies the following formulae (1) to (4):0.65≦W(A+D)/W(T)≦0.99  (1) 0.01≦W(B+C)/W(T)≦0.35  (2)0.02≦W(A)/W(A+D)≦0.98  (3) 0.04≦W(B)/W(B+C)≦0.96  (4).
 21. The resincomposition according to claim 1, wherein the compositional ratio byweight satisfies the following formulae (1) to (4):0.70≦W(A+D)/W(T)≦0.985  (1) 0.015≦W(B+C)/W(T)≦0.30  (2)0.03≦W(A)/W(A+D)≦0.97  (3) 0.05≦W(B)/W(B+C)≦0.95  (4).